Luminescent manganese (II) complex capable of being activated at high and low temperatures as well as preparation method and application of luminescent manganese (II) complex

Abstract

The invention relates to the technical field of organic photoelectric functional materials, in particular to a luminous manganese (II) complex capable of being activated at high and low temperatures as well as a preparation method and application thereof. The structural formula of the luminous manganese (II) complex is one or more of the following formulas: # imgabs0 #, wherein X is Cl, Br or I. The invention further discloses a preparation method of the luminous manganese (II) complex. A plurality of alkoxy chains are introduced to the molecule of the manganese (II) complex provided by the invention, so that water molecules in the air can be adsorbed, and the luminescence characteristic of the manganese (II) complex material can be controlled at double temperatures. According to the invention, the luminous intensity of the two manganese (II) complex materials can be obviously enhanced by reducing and increasing the temperature. Besides, by utilizing the high and low temperature luminescence activation characteristics of the manganese (II) complex, the safe anti-counterfeit label can be prepared, so that the application of the manganese (II) complex material in the field of information safety is greatly promoted. In addition, high-safety binary code information is developed by using a manganese (II) complex material, and decryption and reading of the information are realized by using temperature.

Description

Technical Field

[0001] The invention relates to the technical field of organic photoelectric functional materials, and in particular to a luminescent manganese (II) complex capable of being activated at high and low temperatures, a preparation method and an application thereof. Background Art

[0002] As an emerging class of luminescent materials, phosphorescent manganese (II) complexes have the advantages of high photoluminescence quantum efficiency, low cost, low toxicity and simple synthesis, and have been widely used in 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 difficult to regulate. At present, a few ionic manganese (II) complexes quench the luminescence of manganese (II) complexes by adsorbing small guest molecules (including water, methanol and ethylene glycol). So far, the simultaneous activation of luminescence of manganese (II) complexes by high and low temperature stimulation has not been reported. Summary of the invention

[0003] In view of the above-mentioned deficiencies in the prior art, the purpose of the present invention is to provide a luminescent manganese (II) complex that can be activated at high and low temperatures, a preparation method and its application, aiming to develop a manganese (II) complex with high and low temperature luminescent activation characteristics, and expand the application of manganese (II) complexes in the security field.

[0004] The technical solution of the present invention is as follows:

[0005] In a first aspect of the present invention, a luminescent manganese (II) complex that can be activated at high and low temperatures is provided, wherein the structural formula of the luminescent manganese (II) complex is one or more of the following:

[0006]

[0007] Wherein, X=Cl, Br or I.

[0008] Optionally, the structural formula of the luminescent manganese (II) complex is one or both of the following:

[0009]

[0010] The second aspect of the present invention provides a method for preparing the luminescent manganese (II) complex that can be activated at high and low temperatures, which comprises the steps of:

[0011] Provided is DEtPO, wherein the structural formula of the DEtPO is

[0012] Under an inert atmosphere, the DEtPO and the tetrahydrated manganese halide are mixed in a first solvent, and stirred at 50-60° C. for 6-10 h to obtain DEtPO-MnX2;

[0013] Alternatively, a DISPO is provided, wherein the DISPO has a structural formula of

[0014] Under an inert atmosphere, the DISPO and tetrahydrated manganese halide are mixed in a second solvent and stirred at 50-60° C. for 6-10 h to obtain DISPO-MnX2.

[0015] Optionally, the first solvent is at least one of methanol and ethanol;

[0016] The DEtPO and the manganese halide tetrahydrate are 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] The third aspect of the present invention provides the use of the luminescent manganese (II) complex that can be activated at high and low temperatures in security and anti-counterfeiting.

[0020] In a fourth aspect of the present invention, an anti-counterfeiting label is provided, wherein the anti-counterfeiting label is prepared on filter paper by including the luminescent manganese (II) complexes DEtPO-MnX2 and DMePO-MnX2 that can be activated at high and low temperatures as described in the present invention;

[0021] Alternatively, the anti-counterfeiting label is prepared on filter paper by including the luminescent manganese (II) complexes DISPO-MnX2 and DMePO-MnX2 that can be activated at high and low temperatures as described in the present invention;

[0022] Wherein, when X in DMePO-MnX2 is Br, the structural formula of the DMePO-MnX2 is

[0023] The fifth aspect of the present invention provides the use of the luminescent manganese (II) complex that can be activated at high and low temperatures in information security.

[0024] Optionally, the information security includes decryption and reading of information.

[0025] Beneficial effects: The present invention provides two neutral manganese (II) complex materials with luminescent activation properties. Compared with the existing neutral manganese (II) complex materials, the manganese (II) complex molecules provided by the present invention introduce multiple alkoxy chains, which are beneficial to the adsorption of water molecules in the air, thereby realizing the dual-temperature controlled luminescent properties of the manganese (II) complex materials. The present invention can significantly enhance the luminescent intensity of the two manganese (II) complex materials by lowering and raising the temperature. In addition, by utilizing its high and low temperature luminescent activation characteristics, security anti-counterfeiting labels can be prepared, which greatly promotes the application of manganese (II) complex materials in the field of information security. In addition, high-security binary code information has been developed using manganese (II) complex materials, and temperature is used to achieve decryption and reading of information. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 Schematic diagram of the crystal structure of DEtPO-MnBr2 in Example 1 of the present invention.

[0027] Figure 2 This is a graph showing the luminescence spectrum change of DEtPO-MnBr2 with increasing temperature in Example 1 of the present invention, wherein the illustrations are photos of DEtPO-MnBr2 at room temperature and high temperature, and the direction of the black dotted arrow is the direction of increasing temperature.

[0028] Figure 3 This is a graph showing the change in the luminescence spectrum of DEtPO-MnBr2 as the temperature decreases in Example 1 of the present invention, wherein the inset is a photograph of DEtPO-MnBr2 at room temperature and low temperature, and the direction of the black dotted arrow is the direction of temperature decrease.

[0029] Figure 4 This is a diagram of a high-temperature anti-counterfeiting label in Example 1 of the present invention.

[0030] Figure 5 This is a high-security binary code information diagram in Example 1 of the present invention, wherein a is a schematic diagram of preparing an encryption diagram with different materials, b is a luminescent image at different temperatures and under ultraviolet light, and c is a schematic diagram of information encryption and decryption based on the luminescent image. DETAILED DESCRIPTION

[0031] The present invention provides a luminescent manganese (II) complex that can be activated at high and low temperatures, a preparation method and an application thereof. In order to make the purpose, technical scheme and effect of the present invention clearer and more specific, the present invention is further described in detail below. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0032] The embodiment of the present invention provides a luminescent manganese (II) complex that can be activated at high and low temperatures, wherein the structural formula of the luminescent manganese (II) complex is one or more of the following:

[0033]

[0034] Wherein, X=Cl, Br or I.

[0035] In an embodiment of the present invention, two neutral manganese (II) complex materials with luminescent activation properties are provided. Compared with the existing neutral manganese (II) complex materials, multiple alkoxy chains are introduced into the manganese (II) complex molecules provided in the embodiment of the present invention, and water molecules and oxygen atoms in the alkoxy chains can form hydrogen bonds, which adsorb water molecules in the air through hydrogen bonds, and the non-radiative transition of the vibration of the alkoxy chains and water molecules in the molecules makes the manganese (II) complex present very weak luminescence under normal conditions. At low temperatures, the vibration of the molecular system is suppressed, so that the luminescence intensity of the manganese (II) complex is significantly enhanced; at high temperatures, the water molecules are removed, and the luminescence of the manganese (II) complex is also enhanced, thereby realizing the dual-temperature control of the luminescence characteristics of the manganese (II) complex material.

[0036] In the embodiment of the present invention, the luminescence intensity of the two manganese (II) complex materials can be significantly enhanced by lowering the temperature and raising the temperature. In addition, by utilizing the high and low temperature luminescence activation characteristics, security anti-counterfeiting labels can be prepared, which greatly promotes the application of manganese (II) complex materials in the field of information security. In addition, high-security binary code information is developed using manganese (II) complex materials, and the decryption and reading of information are achieved by utilizing temperature.

[0037] In one embodiment, the structural formula of the luminescent manganese (II) complex is one or both of the following:

[0038]

[0039] Both compounds, DEtPO-MnBr2 and DISPO-MnBr2, exhibit temperature-controlled luminescence activation properties.

[0040] The embodiment of the present invention provides a method for preparing the luminescent manganese (II) complex that can be activated at high and low temperatures, which comprises the steps of:

[0041] Provided is DEtPO, wherein the structural formula of the DEtPO is

[0042] Under an inert atmosphere, the DEtPO and tetrahydrated manganese halide are mixed in a first solvent, and stirred at 50-60° C. for 6-10 h (eg, 8 h) 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 the manganese halide tetrahydrate are mixed in a first solvent at a molar ratio of 1:1.

[0045] The embodiment of the present invention provides a method for preparing the luminescent manganese (II) complex that can be activated at high and low temperatures, which comprises the steps of:

[0046] Provide a DISPO having a structural formula of

[0047] Under an inert atmosphere, the DISPO and tetrahydrated manganese halide are mixed in a second solvent, and stirred at 50-60° C. for 6-10 h (eg, 8 h) 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 is mixed with manganese halide tetrahydrate in a molar ratio of 1:1 in a second solvent.

[0050] The embodiment of the present invention provides the application of the luminescent manganese (II) complex that can be activated at high and low temperatures in security and anti-counterfeiting.

[0051] An embodiment of the present invention provides an anti-counterfeiting label, wherein the anti-counterfeiting label is prepared on filter paper by including the luminescent manganese (II) complexes DEtPO-MnX2 and DMePO-MnX2 that can be activated at high and low temperatures as described in the embodiment of the present invention;

[0052] Alternatively, the anti-counterfeiting label is prepared on filter paper by including the luminescent manganese (II) complexes DISPO-MnX2 and DMePO-MnX2 that can be activated at high and low temperatures as described in the embodiments of the present invention;

[0053] Wherein, when X in DMePO-MnX2 is Br, the structural formula of the DMePO-MnX2 is

[0054] In view of the temperature-controllable luminescence activation behavior of manganese (II) complexes, their potential applications in anti-counterfeiting have been further developed. For example, anti-counterfeiting labels were prepared on filter paper using the reported DMePO-MnBr2 and temperature-activated DEtPO-MnBr2 crystalline powders. Under UV light and room temperature, the pattern only shows partial information, while the complete pattern can be read under UV light and high temperature.

[0055] The embodiment of the present invention provides the application of the luminescent manganese (II) complex that can be activated at high and low temperatures 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 by means of specific examples.

[0058] Since the synthesis methods and photophysical properties of DEtPO-MnBr2 and DISPO-MnBr2 are similar, DEtPO-MnBr2 will be used as an example for detailed description below.

[0059] Example 1: Preparation, characterization, testing and application of compound DEtPO-MnBr2

[0060] 1. Preparation of compound DEtPO-MnBr2, the preparation method thereof 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 distilled under reduced pressure to dryness, and then 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 then manganese bromide tetrahydrate was added at a molar ratio of 1:1, stirred at 50°C for 8h, and then distilled under reduced pressure and dried to obtain the complex DEtPO-MnBr2.

[0065] 2. Characterization and photophysical properties of DEtPO-MnBr2

[0066] DEtPO-MnBr2 was dissolved in a mixed solvent of dichloromethane and ethyl acetate, DEtPO-MnBr2 single crystals were collected by slow evaporation, and its single crystal structure was obtained, as shown in FIG. Figure 1 shown.

[0067] The luminescence spectrum of DEtPO-MnBr2 powder was tested as the temperature increased. The inset is a photo of DEtPO-MnBr2 at room temperature (300K) and high temperature (420K). Figure 2 As shown. Figure 2 It can be seen that with the increase of temperature, the luminescence intensity of DEtPO-MnBr2 powder gradually increases, indicating that it has the ability to activate the luminescent crystallization of manganese (II) complexes at high temperature.

[0068] The luminescence spectrum of DEtPO-MnBr2 powder was tested as the temperature decreased. The inset is a photo of DEtPO-MnBr2 at room temperature (300K) and low temperature (200K). Figure 3 As shown. Figure 3 It can be seen that as the temperature decreases, the luminescence intensity of DEtPO-MnBr2 powder gradually increases, indicating that it has the ability to activate the luminescent crystallization of manganese (II) complexes at low temperature.

[0069] 3. Application in anti-counterfeiting and information security

[0070] Since DEtPO-MnBr2 has a unique temperature-controlled luminescence activation behavior, its potential application in anti-counterfeiting is further developed. The specific operation steps are as follows: the anti-counterfeiting label is prepared on filter paper using the reported DMePO-MnBr2 and temperature-activated DEtPO-MnBr2 crystal powder. Under ultraviolet light and room temperature, the pattern only shows part of the information, while under ultraviolet light and high temperature, the complete pattern can be read (see Figure 4 ).

[0071] In addition, high-security binary code information was developed using DEtPO, DMePO-MnBr2, and DEtPO-MnBr2. Figure 5 As shown in a, b and c, the points that emit green light are defined as output codes "1", otherwise the output codes are all "0". Under ultraviolet irradiation 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 strong green light, allowing the binary code to be re-decoded into the true information "POLYU". Therefore, these results show 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 the present invention has high and low temperature luminescence activation characteristics; high-temperature information display is achieved using DEtPO-MnBr2 and the 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 above examples. For ordinary technicians in this field, improvements or changes can be made based on the above description. All these improvements and changes should fall within the scope of protection of the claims attached to the present invention.

Claims

1. A luminescent manganese (II) complex that can be activated at high and low temperatures, characterized in that: The structural formula of the luminescent manganese (II) complex is one or more of the following: Wherein, X=Cl, Br or I.

2. The luminescent manganese (II) complex capable of high and low temperature activation according to claim 1, characterized in that: The structural formula of the luminescent manganese (II) complex is one or both of the following:

3. A method for preparing the luminescent manganese (II) complex capable of high and low temperature activation according to claim 1, characterized in that: Includes steps: Provided is DEtPO, wherein the structural formula of the DEtPO is Under an inert atmosphere, the DEtPO and the tetrahydrated manganese halide are mixed in a first solvent, and stirred at 50-60° C. for 6-10 h to obtain DEtPO-MnX2; Alternatively, a DISPO is provided, wherein the DISPO has a structural formula of Under an inert atmosphere, the DISPO and tetrahydrated manganese halide are mixed in a second solvent and stirred at 50-60° C. for 6-10 h to obtain DISPO-MnX2.

4. The method for preparing a luminescent manganese (II) complex that can be activated at high and low temperatures according to claim 3, characterized in that: The first solvent is at least one of methanol and ethanol; The DEtPO and the manganese halide tetrahydrate are mixed in a first solvent at a molar ratio of 1:

1.

5. The method for preparing a luminescent manganese (II) complex that can be activated at high and low temperatures 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. Use of the luminescent manganese (II) complex capable of high or low temperature activation as claimed in any one of claims 1 to 2 in security and anti-counterfeiting.

7. An anti-counterfeiting label, characterized in that: The anti-counterfeiting label is prepared on filter paper by including the luminescent manganese (II) complexes DEtPO-MnX2 and DMePO-MnX2 that can be activated at high and low temperatures 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 that can be activated at high and low temperatures as described in claim 1; Wherein, when X in DMePO-MnX2 is Br, the structural formula of the DMePO-MnX2 is 8. Use of the luminescent manganese (II) complex capable of high or low temperature activation as claimed in any one of claims 1 to 2 in information security.

9. The use according to claim 8, characterized in that: The information security includes decryption and reading of information.

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