One-dimensional copper-based luminescent material with temperature response as well as preparation method and application of one-dimensional copper-based luminescent material

Abstract

The invention belongs to the technical field of luminescent materials, and particularly relates to a one-dimensional copper-based luminescent material with temperature response and a preparation method and application thereof, a novel copper-based organic-inorganic hybrid perovskite material provided by the invention has the characteristics of double excitation and single emission at room temperature, and the structure is subjected to certain structural transformation in a cooling process, so that the luminescent material can be applied to the field of luminescent materials. A single structure shows double-excitation and double-emission fluorescence properties at low temperature; the material is simple in synthesis method, low in raw material toxicity, good in luminescence performance stability, high in anti-counterfeiting capability and applicable to the field of anti-counterfeiting.

Description

Technical Field

[0001] The present invention belongs to the technical field of luminescent materials, and in particular relates to a one-dimensional copper-based luminescent material with temperature response, a preparation method and an application thereof. Background Art

[0002] Among organic-inorganic hybrid perovskites, lead (Pb)-based perovskites have been extensively explored in different materials due to their excellent optoelectronic properties. However, the high toxicity of this type of material has always been a problem that hinders its practical application. In order to solve the above problems, researchers have adopted a variety of methods: one is to use polymers or other types of materials to wrap to avoid the leakage of Pb; Cu, Mn, Sn, In, Sb, etc. can also be used to replace Pb to synthesize different types of organic-inorganic hybrid perovskite materials. Among these materials, Cu(I)-based organic-inorganic hybrid perovskite materials have low cost, low toxicity, rich variable coordination modes, and good optoelectronic properties and have been widely studied. Among them, some materials show a response to temperature stimulation. Under certain temperature conditions, the fluorescence emission of the material usually has a reversible change. For example, the organic-inorganic hybrid perovskite (TPA)CuBr2(TPA + =[N(CH2CH2CH3)4] + ), which can be converted into (TPA)2Cu4Br6 under external water stimulation, and the luminescence color changes from cyan to orange under ultraviolet light. In addition, (TPA)CuBr2 and (TPA)2Cu4Br6 show reversible "on-off" luminescence phenomenon and cyclic stability under thermal stimulation.

[0003] However, both (TPA)CuBr2 and (TPA)2Cu4Br6 are single-emission materials, and their cycle life is relatively low. Although Cu(I)-based organic-inorganic hybrid perovskite materials have made rapid progress, due to their ionic properties, they are generally sensitive to moisture and air and easily absorb water and decompose in humid environments. In addition, Cu(I) is easily oxidized by oxygen, which can easily lead to irreversible decomposition reactions. Therefore, the number of reversible cycles still needs to be improved. Therefore, it is of great significance to develop Cu(I)-based organic-inorganic hybrid perovskite materials with higher stability. Summary of the Invention

[0004] The present invention provides a one-dimensional copper-based luminescent material with temperature response, a preparation method thereof, and an application thereof.

[0005] The technical solutions of the present invention are as follows:

[0006] The present invention provides a one-dimensional copper-based luminescent material with temperature response, wherein the luminescent material is C 11 N3H 30 Cu3I6、C 11 N3H30 Cu 3.085-3.103 I 6.079-6.1 .

[0007] The C 11 N3H 30 Cu3I6, at room temperature, excitation wavelengths are 283nm and 322nm, and emission wavelength is 508nm;

[0008] The C 11 N3H 30 Cu 3.085-3.103 I 6.079-6.1 , the excitation wavelengths are 283nm and 342nm, and the emission wavelengths are 515nm and 611nm.

[0009] The C 11 N3H 30 Cu 3.085-3.103 I 6.079-6.1 , is C 11 N3H 30 It is obtained by cooling Cu3I6 to below 253K.

[0010] The C 11 N3H 30 Cu3I6, three Cu are bonded to form a Cu3 skeleton in the shape of a regular triangle, and six I - After coordination, an inorganic skeleton is formed. The protonated 2,6,10-trimethyl-2,6,10-triazaundecane ligand surrounds the inorganic skeleton, and the adjacent Cu3 skeleton is composed of I - After connecting, they form a one-dimensional chain structure.

[0011] The C 11 N3H 30 Cu3I6 belongs to the monoclinic crystal system and its space group is P21 / n.

[0012] The C 11 N3H 30 Cu 3.085-3.103 I 6.079-6.1 , including: C 11 N3H 30 Cu 3.085 I 6.087 、C 11 N3H 30 Cu 3.098 I 6.087 、C 11 N3H 30 Cu 3.085 I 6.088 、C 11 N3H 30 Cu 3.094 I 6.079 、C11 N3H 30 Cu 3.103 I 6.083 .

[0013] The present invention also provides a method for preparing a one-dimensional copper-based luminescent material with temperature response, comprising:

[0014] 2,6,10-trimethyl-2,6,10-triazaundecane, cuprous iodide, hydroiodic acid, hypophosphorous acid, ethanol and acetonitrile are mixed, the mixture is dissolved under ultrasound assistance at room temperature, and then heated, cooled, washed and dried to obtain a product.

[0015] The molar ratio of the 2,6,10-trimethyl-2,6,10-triazaundecane to cuprous iodide is 1.1:1; the volume ratio of the hydroiodic acid, hypophosphorous acid, ethanol, and acetonitrile is 3:0.5:3:5; and the molar and volume ratio of the cuprous iodide to hydroiodic acid is 1 mmol:3 mL.

[0016] The heating temperature is 90°C.

[0017] The present invention also provides an application of a temperature-responsive one-dimensional copper-based luminescent material in anti-counterfeiting materials.

[0018] Beneficial effects

[0019] The present invention provides a novel copper-based organic-inorganic hybrid perovskite material, which has the characteristics of dual excitation and single emission at room temperature. During the cooling process, the structure undergoes a certain structural transformation, and the single structure exhibits the fluorescence properties of dual excitation and dual emission at low temperatures. In addition, the synthesis method of the material is simple, the raw materials have low toxicity, and the luminescence performance exhibits good stability. Therefore, it is used in the anti-counterfeiting field and has strong anti-counterfeiting capabilities. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 This is the X-ray diffraction pattern of [PMDETA]Cu3I6.

[0021] Figure 2 (a) is a schematic diagram of the single crystal structure of [PMDETA]Cu3I6, (b) is the excitation and emission diagram at room temperature, (c) is the three-dimensional fluorescence spectrum, (d) is the color coordinate, (e) is the fluorescence lifetime, and (f) is the relationship between excitation power and fluorescence emission intensity.

[0022] Figure 3 This is the quantum yield test diagram of [PMDETA]Cu3I6 single crystal.

[0023] Figure 4(a) is a photograph of the [PMDETA]Cu3I6 single crystal changing with temperature under excitation at different wavelengths, (b) is the excitation and emission diagram at 80K, (c) is the change of the crystal emission intensity with the temperature increase process under 283nm excitation, and (d) is the change of the crystal emission intensity with the temperature increase process under 342nm excitation.

[0024] Figure 5 Schematic diagram of the design of anti-counterfeiting patterns using [PMDETA]Cu3I6 single crystals and reported (BACQ)2MnCl4 single crystals.

[0025] Figure 6 This is the “cooling-heating” stability test result of the crystal.

[0026] Figure 7 The emission pattern (a) and X-ray diffraction pattern (b) of [PMDETA]Cu3I6 single crystal after immersion in water, and the emission pattern (c) and X-ray diffraction pattern (d) after immersion in solvents of different polarities. DETAILED DESCRIPTION

[0027] The following examples are intended to illustrate the present invention rather than to further limit the present invention.

[0028] The present invention provides a one-dimensional copper-based luminescent material with temperature response, wherein the luminescent material is C 11 N3H 30 Cu3I6、C 11 N3H 30 Cu 3.085-3.103 I 6.079-6.1 .

[0029] The C 11 N3H 30 Cu3I6, at room temperature, such as 300K, has excitation wavelengths of 283nm and 322nm, and an emission wavelength of 508nm;

[0030] The C 11 N3H 30 Cu 3.085-3.103 I 6.079-6.1 , the excitation wavelengths are 283nm and 342nm, and the emission wavelengths are 515nm and 611nm.

[0031] Furthermore, the C 11 N3H 30 Cu 3.085-3.103 I 6.079-6.1 , is C 11 N3H 30 It is obtained by cooling Cu3I6 to below 253K.

[0032] About C 11N3H 30 Cu 3.085-3.103 I 6.079-6.1 , including: C 11 N3H 30 Cu 3.085 I 6.087 、C 11 N3H 30 Cu 3.098 I 6.087 、C 11 N3H 30 Cu 3.085 I 6.088 、C 11 N3H 30 Cu 3.094 I 6.079 、C 11 N3H 30 Cu 3.103 I 6.083 .

[0033] That is, the luminescent material C of the present invention 11 N3H 30 Cu3I6 has the characteristics of dual excitation and single emission at room temperature. As the temperature decreases, the characteristics of dual excitation and dual emission appear. In other words, the C 11 N3H 30 Cu 3.1 I 6.1 with C 11 N3H 30 Cu 3.085-3.103 I 6.079-6.1 and the corresponding fluorescence properties transformation.

[0034] In the crystal structure, the C 11 N3H 30 Cu3I6, three Cu are bonded to form a Cu3 skeleton in the shape of a regular triangle, and six I - After coordination, an inorganic skeleton is formed. The protonated 2,6,10-trimethyl-2,6,10-triazaundecane ligand surrounds the inorganic skeleton, and the adjacent Cu3 skeleton is composed of I - After connecting, they form a one-dimensional chain structure.

[0035] In addition, the C 11 N3H 30 Cu3I6 belongs to the monoclinic crystal system and its space group is P21 / n.

[0036] The present invention also provides a method for preparing the temperature-responsive one-dimensional copper-based luminescent material, comprising:

[0037] 2,6,10-trimethyl-2,6,10-triazaundecane, cuprous iodide, hydroiodic acid, hypophosphorous acid, ethanol and acetonitrile are mixed, the mixture is dissolved under ultrasound assistance at room temperature, and then heated, cooled, washed and dried to obtain a product.

[0038] In terms of the amount of raw materials added, the molar ratio of the 2,6,10-trimethyl-2,6,10-triazaundecane to cuprous iodide is 1.1:1; the volume ratio of the hydroiodic acid, hypophosphorous acid, ethanol and acetonitrile is 3:0.5:3:5; and the molar and volume ratio of the cuprous iodide to hydroiodic acid is 1 mmol:3 mL.

[0039] In terms of process parameters, the heating temperature is 90°C.

[0040] It can be seen that the synthesis method of the present invention is simple, easy to operate, and the raw materials have low toxicity.

[0041] The present invention also provides an application of the temperature-responsive one-dimensional copper-based luminescent material in anti-counterfeiting materials.

[0042] Specifically, the anti-counterfeiting material is used to make ASCII code.

[0043] The present invention provides a novel copper-based organic-inorganic hybrid perovskite material, which has the characteristics of dual excitation and single emission at room temperature. During the cooling process, the structure undergoes a certain structural transformation, and the single structure exhibits the fluorescence properties of dual excitation and dual emission at low temperatures. In addition, the synthesis method of the material is simple, the raw materials have low toxicity, and the luminescence performance exhibits good stability. Therefore, it is used in the anti-counterfeiting field and has strong anti-counterfeiting capabilities.

[0044] Example 1

[0045] The raw materials used were all commercially available and were not further processed.

[0046] C 11 N3H 30 Synthesis of Cu3I6: Combine 2,6,10-trimethyl-2,6,10-triazaundecane (1.1 mmol, 0.22 g), CuI (1 mmol, 0.19 g), hydroiodic acid (3 mL), hypophosphorous acid (0.5 mL), ethanol (3 mL), and acetonitrile (5 mL). The mixture was transferred to a 20 mL glass sample and dissolved under ultrasound at room temperature for 10 minutes. The mixture was then heated at 90°C for 4 days. After cooling to room temperature, the crystals precipitated and were filtered, washed three times with ether, and stored dry (0.5 mL). This was designated [PMDETA]Cu3I6.

[0047] On this basis, when the temperature is lowered to different temperatures, its structure undergoes the following changes: C 11 N3H 30 Cu3.085 I 6.087 (253K), C 11 N3H 30 Cu 3.098 I 6.087 (213K), C 11 N3H 30 Cu 3.085 I 6.088 (173K), C 11 N3H 30 Cu 3.094 I 6.079 (133K), C 11 N3H 30 Cu 3.103 I 6.083 (93K). They are respectively denoted as [PMDETA]Cu 3.085 I 6.087 ,[PMDETA]Cu 3.098 I 6.087 ,[PMDETA]Cu 3.085 I 6.088 ,[PMDETA]Cu 3.094 I 6.079 ,[PMDETA]Cu 3.103 I 6.083 .

[0048] Experimental results

[0049] The C obtained in Example 1 11 N3H 30 Cu3I6, i.e. [PMDETA]Cu3I6, was subjected to the following characterization and analysis.

[0050] 1. Crystal structure characterization

[0051] [PMDETA]Cu3I6 single crystal data (Table 1) and powder X-ray diffraction data ( Figure 1 ) verified the chemical formula, and the results showed that the single crystal [PMDETA]Cu3I6 (296.15K) is a P21 / n monoclinic intergroup (Table 1). In the single crystal structure, three Cu(I)s form a regular triangle after bonding, and six iodine anions (I - ) is coordinated with it, and the protonated 2,6,10-trimethyl-2,6,10-triazaundecane ligand surrounds the inorganic framework. The adjacent equilateral triangle Cu3 skeleton is composed of I - The negative ions are connected to form a one-dimensional chain structure ( Figure 2 (a)).

[0052] C 11 N3H 30The Cu3I6 single crystal test conditions are set to different low temperature environments, and the corresponding single crystal structures C 11 N3H 30 Cu 3.1 I 6.1 (253K), C 11 N3H 30 Cu 3.1 I 6.1 (213K), C 11 N3H 30 Cu 3.1 I 6.1 (173K), C 11 N3H 30 Cu 3.1 I 6.1 (133K), C 11 N3H 30 Cu 3.1 I 6.1 (93K) (Table 1).

[0053] As can be seen from Table 1, when the temperature is lower than 253K, different temperatures correspond to different structures, but the difference in crystal structure is not too large.

[0054] Table 1 Single crystal data at different temperatures

[0055]

[0056]

[0057] a R1=∑||F o |-|F c || / ∑|F o |. b wR2=[∑w(F o 2 -F c 2 ) 2 / ∑w(F o 2 ) 2 ] 1 / 2 .

[0058] 2. Characterization of crystal fluorescence properties

[0059] like Figure 2 As shown in (b), at room temperature, the [PMDETA]Cu3I6 single crystal has two main excitation peaks, 283nm and 322nm, and the emission peak is 508nm.

[0060] The three-dimensional fluorescence spectrum further verified the maximum excitation peak (λ ex) and emission peak (λ em ) are 322nm and 508nm respectively ( Figure 2 (c)).

[0061] The International Commission on Illumination (CIE) color coordinates are (0.24, 0.45) ( Figure 2 (d)).

[0062] The fluorescence lifetime of the crystal is 1.480 μs, which is consistent with the characteristics of Cu(I) halide ( Figure 2 (e)).

[0063] Depend on Figure 2 As shown in (f), the excitation power and the fluorescence intensity have a good linear relationship, R 2 The value of 0.96916 indicates that the luminescence phenomenon is not caused by permanent defects within the material. In materials science and spectroscopy research, this analysis helps to understand the luminescence mechanism of materials.

[0064] Depend on Figure 3 It can be seen that under 322 nm wavelength excitation, the quantum yield (PLQY) of the crystal measured at 300 K is 30.55%.

[0065] 3. Characterization of crystal fluorescence changes with temperature

[0066] As the temperature drops from 300K to 80K, the luminescent color of the crystal gradually changes under different excitation wavelengths. Figure 4 As shown in (a), under 254nm ultraviolet light, the luminescent color of the crystal changes from yellow-green to dark green. Under 365nm ultraviolet light, the luminescent color of the crystal changes from yellow-green to dark red.

[0067] Based on the above phenomenon, the excitation and emission spectra at 80K were further measured. Figure 4 As shown in (b), under excitation at 283 nm and 342 nm wavelengths, the emission wavelengths of the crystal are 515 nm and 611 nm, respectively.

[0068] Then we further characterized the ex =283nm), the emission wavelength of the crystal changes during the heating process. Figure 4 As shown in (c), during the above-mentioned heating process, the center of its maximum emission wavelength undergoes a slight red shift.

[0069] Figure 4 (d) shows that during the heating process, the 342nm wavelength excitation (λ ex =342nm), the emission wavelength center of the crystal undergoes a more obvious blue shift.

[0070] 4. Application of crystals in anti-counterfeiting

[0071] [PMDETA]Cu3I6 single crystal and the reported (BACQ)2MnCl4 (i.e. (C 13 H 16 Anti-counterfeiting ASCII patterns were fabricated from (BACQ)2MnCl4 single crystal powder. The previously reported (BACQ)2MnCl4 emits green light under UV excitation at 369nm and 254nm. The [PMDETA]Cu3I6 single crystal of this application, however, emits green light under UV excitation at 369nm and 254nm at 300K, and red and green light, respectively, under UV excitation at 369nm and 254nm at 80K.

[0072] like Figure 5 As shown, both materials emit no light under fluorescent light. However, at room temperature (300K), when illuminated by a 365nm UV lamp, they both emit yellow-green light. Subsequently, when the temperature is gradually lowered to 80K, the luminescence color of (BACQ)2MnCl4 remains virtually unchanged. Meanwhile, the luminescence color of [PMDETA]Cu3I6 crystals changes from green to yellow, orange-red, and red, thus enabling anti-counterfeiting applications.

[0073] 5. Crystal stability characterization

[0074] After the crystal went through 20 reversible cooling-heating processes, the luminous intensity of red and green light remained almost unchanged, which proved the good stability of the crystal ( Figure 6 ).

[0075] After [PMDETA]Cu3I6 single crystal was immersed in water for different time (5, 24, 36, 48 hours), the emission spectrum ( Figure 7 (a)) and X-ray diffraction pattern ( Figure 7 There is almost no significant change in (b), indicating that the crystals have high water stability.

[0076] [PMDETA]Cu3I6 crystals were immersed in different polar solvents: acetone, acetonitrile, tertiary butanol, sec-butanol, isobutanol, isopropanol, n-propanol, ethylene glycol, ethanol, methanol for 14 days. Although the emission spectra showed some differences ( Figure 7 (c)), but through X-ray diffraction analysis, it can be seen that ( Figure 7In (d), the main peaks of the crystal structure still exist, which indicates that the crystals have good solvent stability.

Claims

1. A one-dimensional copper-based luminescent material with temperature response, characterized in that: The luminescent material is C 11 N3H 30 Cu3I6、C 11 N3H 30 Cu 3.085-3.103 I 6.079-6.1 .

2. The temperature-responsive one-dimensional copper-based luminescent material according to claim 1, characterized in that: The C 11 N3H 30 Cu3I6, at room temperature, excitation wavelengths are 283nm and 322nm, and emission wavelength is 508nm; The C 11 N3H 30 Cu 3.085-3.103 I 6.079-6.1 , the excitation wavelengths are 283nm and 342nm, and the emission wavelengths are 515nm and 611nm.

3. The temperature-responsive one-dimensional copper-based luminescent material according to claim 1, wherein: The C 11 N3H 30 Cu 3.085-3.103 I 6.079-6.1 , is C 11 N3H 30 It is obtained by cooling Cu3I6 to below 253K.

4. The one-dimensional copper-based luminescent material with temperature response according to claim 1, characterized in that The C 11 N3H 30 Cu3I6, three Cu are bonded to form a Cu3 skeleton in the shape of a regular triangle, and six I - After coordination, an inorganic skeleton is formed. The protonated 2,6,10-trimethyl-2,6,10-triazaundecane ligand surrounds the inorganic skeleton, and the adjacent Cu3 skeleton is composed of I - After connecting, they form a one-dimensional chain structure.

5. The one-dimensional copper-based luminescent material with temperature response according to claim 1, characterized in that: The C 11 N3H 30 Cu3I6 belongs to the monoclinic crystal system and its space group is P21 / n.

6. The temperature-responsive one-dimensional copper-based luminescent material according to claim 1, characterized in that: The said C 11 N3H 30 Cu 3.085-3.103 I 6.079-6.1 , including: C 11 N3H 30 Cu 3.085 I 6.087 、C 11 N3H 30 Cu 3.098 I 6.087 、C 11 [[ID=二十六]]N3H 30 Cu 3.085 I 6.088 、C 11 N3H 30 ... Cu 3.094 I 6.079 、C 11 N3H 30 Cu 3.103 I 6.083 。 It should be noted that the content seems to be a bit repetitive and might be incomplete or have some formatting issues in the original. The translation is done based on the provided text as accurately as possible while maintaining the tags and structure.

7. A method for preparing a one-dimensional copper-based luminescent material with temperature response according to claim 1, characterized in that: include: 2,6,10-trimethyl-2,6,10-triazaundecane, cuprous iodide, hydroiodic acid, hypophosphorous acid, ethanol and acetonitrile are mixed, the mixture is dissolved under ultrasound assistance at room temperature, and then heated, cooled, washed and dried to obtain a product.

8. The method for preparing a one-dimensional copper-based luminescent material with temperature response according to claim 7, characterized in that: The molar ratio of the 2,6,10-trimethyl-2,6,10-triazaundecane to cuprous iodide is 1.1:1; the volume ratio of the hydroiodic acid, hypophosphorous acid, ethanol, and acetonitrile is 3:0.5:3:5; and the molar and volume ratio of the cuprous iodide to hydroiodic acid is 1 mmol:3 mL.

9. The method for preparing a one-dimensional copper-based luminescent material with temperature response according to claim 7, characterized in that: The heating temperature is 90°C.

10. Use of the temperature-responsive one-dimensional copper-based luminescent material according to any one of claims 1 to 6 or the temperature-responsive one-dimensional copper-based luminescent material prepared by the preparation method according to any one of claims 7 to 9 in anti-counterfeiting materials.

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