Metal-polynitrogen heterocyclic complex glass material with adjustable phosphorescent color and preparation method thereof

Abstract

The invention discloses a phosphorescence color adjustable metal-polynitrogen heterocyclic complex glass material and a preparation method thereof. According to the invention, a series of color-adjustable super-long RTP metal-polynitrogen heterocyclic complex glass materials are successfully prepared by taking metal halides and polynitrogen heterocyclic ligands as raw materials through a hydrothermal disturbance technology and a simple solvent evaporation method. The glass has high hardness and high transparency, the phosphorescence color can be adjusted from blue to yellow, and the excited state life of the glass is up to 186.7 ms. In addition, the method is simple, convenient, efficient and low in cost, and provides an innovative thought and approach for design and preparation of a novel room-temperature phosphorescent glass material.

Description

Technical Field

[0001] This invention belongs to the field of luminescent material preparation technology, specifically relating to a metal-polynitrogen heterocyclic complex glass material with tunable phosphorescence color and its preparation method. Background Technology

[0002] Molecularly persistent luminescent materials, especially ultralong room-temperature phosphorescent (RTP) materials, have attracted much attention in recent years in fields such as optical sensors, anti-counterfeiting technology, photodynamic therapy, and display devices. To achieve efficient persistent luminescence, researchers typically construct rigid environments to immobilize the phosphor, thereby limiting non-radiative decay and facilitating the realization of ultralong RTPs. Currently, research on ultralong RTP materials focuses primarily on materials in the form of powders, crystals, and thin films. However, these forms have limitations in large-scale and macroscopic applications, restricting the scope of practical applications.

[0003] Meanwhile, glass materials (including metallic, inorganic, organic, and polymer glasses) have shown broad application potential in fields such as construction, electronics, energy storage, and medicine due to their high transparency, good formability, and excellent mechanical strength and durability. However, many current glass manufacturing methods, such as melt-quenching and vapor deposition processes, are often time-consuming and energy-intensive. Therefore, developing a simple and environmentally friendly method to fabricate large-size glass at a macroscopic level, enabling easy operation and effective application, is particularly important. Summary of the Invention

[0004] This invention aims to provide a metal-polynitrogen heterocyclic complex glass material with tunable color and ultralong room-temperature phosphorescence (RTP) performance, and its preparation method. In this material, coordination interactions exist between metal ions and ligand molecules, while residual solvent water molecules in the glass participate in strong hydrogen bonding interactions. These strong non-covalent interactions promote the formation of a rigid network structure. Furthermore, hydrothermal disturbances generated during heating and volatilization promote the formation of an amorphous glass structure.

[0005] The preparation method of the phosphorescent color-tunable metal-polynitrogen heterocyclic complex glass material is as follows: metal halide, polynitrogen heterocyclic ligand and concentrated hydrochloric acid are added to deionized water to obtain a mixed solution, and a hydrothermal reaction is carried out at 50-200℃ in a closed manner for 4-10 hours to obtain a clear solution; then the solution is heated at 50-200℃ to remove the solvent to obtain a transparent metal-polynitrogen heterocyclic complex glass material.

[0006] The metal halide is selected from one or more of the transition metals, Group III, IV, V metals, and lanthanides.

[0007] The metal halide is one or more of bromide salts, chloride salts, or double salts.

[0008] The polynitrogen heterocyclic ligands are selected from one or more of the following compounds: .

[0009] The concentration of metal halides in the mixed solution is from 0.002 mol / L to saturation.

[0010] The molar ratio of the polynitrogen heterocyclic ligand to the metal halide is 1-5:1.

[0011] The volume ratio of concentrated hydrochloric acid to deionized water is 0.00001-0.1.

[0012] This invention utilizes metal halides and polynitrogen heterocyclic ligands as raw materials, and successfully prepares a series of color-tunable ultralong RTP metal-polynitrogen heterocyclic complex glass materials through hydrothermal perturbation technology and a simple solvent evaporation method. These glasses exhibit high hardness and high transparency, and their phosphorescence color can be adjusted from blue to yellow, with an excited-state lifetime of up to 186.7 ms. Furthermore, this method is simple, efficient, and inexpensive, providing innovative ideas and approaches for the design and preparation of novel room-temperature phosphorescent glass materials. Attached Figure Description

[0013] Figure 1 It is the Raman spectrum of an indium-1,2,4-triazole complex glass.

[0014] Figure 2 This is the X-ray powder diffraction pattern of an indium-1,2,4-triazole complex glass.

[0015] Figure 3 The differential scanning calorimetry curves are for indium-1,2,4-triazole complex glass.

[0016] Figure 4 The phosphorescence emission spectra of indium-1,2,4-triazole complex glass under different excitation wavelengths are shown.

[0017] Figure 5 The phosphorescence lifetime decay curves of indium-1,2,4-triazole complex glass under different excitation wavelengths are shown. Detailed Implementation

[0018] Example 1 Weigh 0.5 mmol of indium trichloride, weigh 1 mmol of 1,2,4-triazole, and measure 40 μL of concentrated hydrochloric acid (concentration: 36.0%–38.0%). Add these three chemicals to the lining of a reactor containing 15 mL of deionized water. After thorough stirring, place the sealed reactor in an oven at 130°C and heat for 6 h to promote dissolution and obtain a clear solution. Then, place the clear solution in an oven at the same temperature and continue heating with the oven open for 10 h to finally obtain a transparent indium-1,2,4-triazole complex glass.

[0019] The product was characterized as follows: Characterization by high-resolution electrospray ionization mass spectrometry showed that the main component of the glass was a metal-polynitrogen heterocyclic complex.

[0020] Fourier transform infrared spectroscopy tests show that residual solvent water molecules in the glass system participate in hydrogen bonding interactions.

[0021] Nanoindentation tests showed that the glass had a Young's modulus of 5.1 GPa and a hardness of 0.23 GPa.

[0022] Ultraviolet-visible-near-infrared transmission spectroscopy tests show that the glass has a transparency of over 90% in the 500–1400 nm wavelength range.

[0023] Raman spectroscopy analysis revealed that the indium-1,2,4-triazole complex glass at 269 cm⁻¹ −1 The peak at that location is attributed to In-N coordination bonds, such as Figure 1 As shown.

[0024] X-ray powder diffraction analysis revealed that the indium-1,2,4-triazole complex glass exhibits an amorphous structure, such as... Figure 2 As shown.

[0025] Differential scanning calorimetry (DSC) curves show that the glass transition temperature of the indium-1,2,4-triazole complex glass is 63℃, which is higher than room temperature. Figure 3 As shown.

[0026] The phosphorescence emission spectrum shows that when the excitation wavelengths are 254 nm, 295 nm, 365 nm, and 395 nm, the phosphorescence emission peaks of the indium-1,2,4-triazole complex glass appear at 450 nm, 474 nm, 527 nm, and 560 nm, respectively. This indicates that as the excitation wavelength increases, the emission peak gradually red-shifts. Figure 4 As shown.

[0027] The phosphorescence lifetime decay curves show that when the excitation wavelengths are 254 nm, 295 nm, 365 nm, and 395 nm, the phosphorescence lifetimes of the indium-1,2,4-triazole complex glass are 122.8 ms, 180.1 ms, 122.1 ms, and 82.0 ms, respectively. Figure 5 As shown. Example 2

[0028] The preparation method is the same as in Example 1, except that the 1,2,4-triazole is replaced with 4-amino-1,2,4-triazole to obtain indium-4-amino-1,2,4-triazole complex glass.

[0029] The product was characterized as follows: X-ray powder diffraction analysis revealed that the indium-4-amino-1,2,4-triazole complex glass exhibits an amorphous structure.

[0030] Differential scanning calorimetry analysis shows that the glass transition temperature of the indium-4-amino-1,2,4-triazole complex glass is 76℃.

[0031] As can be seen from the phosphorescence emission spectrum, as the excitation wavelength gradually increases from 254 nm to 395 nm, the phosphorescence emission peak of the indium-4-amino-1,2,4-triazole complex glass gradually redshifts.

[0032] The phosphorescence lifetime decay curves show that when the excitation wavelengths are 254 nm, 295 nm, 365 nm, and 395 nm, the phosphorescence lifetimes of the indium-4-amino-1,2,4-triazole complex glass are 176.0 ms, 132.5 ms, 79.9 ms, and 37.2 ms, respectively. Example 3

[0033] The preparation method is the same as in Example 1, except that the 1,2,4-triazole is replaced with 3-carbonyl-1,2,4-triazole to obtain indium-3-carbonyl-1,2,4-triazole complex glass.

[0034] The product was characterized as follows: X-ray powder diffraction analysis revealed that the indium-3-carbonyl-1,2,4-triazole complex glass exhibits an amorphous structure.

[0035] Differential scanning calorimetry analysis shows that the glass transition temperature of the indium-3-carbonyl-1,2,4-triazole complex glass is 55℃.

[0036] As can be seen from the phosphorescence emission spectrum, as the excitation wavelength gradually increases from 254 nm to 395 nm, the phosphorescence emission peak of the indium-3-carbonyl-1,2,4-triazole complex glass gradually red-shifts.

[0037] The phosphorescence lifetime decay curves show that when the excitation wavelengths are 254 nm, 295 nm, 365 nm, and 395 nm, the phosphorescence lifetimes of the indium-3-carbonyl-1,2,4-triazole complex glass are 98.2 ms, 99.4 ms, 99.2 ms, and 58.6 ms, respectively. Example 4

[0038] The preparation method is the same as in Example 1, except that the 1,2,4-triazole is replaced with 1H-tetraazole to obtain indium-1H-tetraazole complex glass.

[0039] The product was characterized as follows: X-ray powder diffraction analysis revealed that the indium-1H-tetrazole complex glass has an amorphous structure.

[0040] Differential scanning calorimetry analysis shows that the glass transition temperature of the indium-1H-tetrazole complex glass is 56℃.

[0041] As can be seen from the phosphorescence emission spectrum, as the excitation wavelength gradually increases from 254 nm to 395 nm, the phosphorescence emission peak of the indium-1H-tetrazole complex glass gradually redshifts.

[0042] The phosphorescence lifetime decay curves show that when the excitation wavelengths are 254 nm, 295 nm, 365 nm, and 395 nm, the phosphorescence lifetimes of the indium-1H-tetrazole complex glass are 40.2 ms, 88.5 ms, 186.7 ms, and 63.3 ms, respectively.

Claims

1. A method for preparing a phosphorescently colored metal-polynitrogen heterocyclic complex glass material, characterized in that, The specific operation of the preparation method is as follows: metal halide, polynitrogen heterocyclic ligand and concentrated hydrochloric acid are added to deionized water to obtain a mixed solution, and a hydrothermal reaction is carried out in a closed system at 50-200℃ for 4-10 hours to obtain a clear solution; then the solution is heated at 50-200℃ to remove the solvent to obtain a transparent metal-polynitrogen heterocyclic complex glass material.

2. The method for preparing the phosphorescently colored tunable metal-polynitrogen heterocyclic complex glass material according to claim 1, characterized in that, The metal halide is selected from one or more of transition metals, Group III, IV, V metals, and lanthanides.

3. The method for preparing the phosphorescently colored tunable metal-polynitrogen heterocyclic complex glass material according to claim 2, characterized in that, The metal halide is one or more of bromide salts, chloride salts, or double salts.

4. The method for preparing the phosphorescently colored metal-polynitrogen heterocyclic complex glass material according to claim 1, characterized in that, The polynitrogen heterocyclic ligands are selected from one or more of the following compounds: .

5. The method for preparing the phosphorescently colored tunable metal-polynitrogen heterocyclic complex glass material according to claim 1, characterized in that, The concentration of metal halides in the mixed solution is from 0.002 mol / L to saturation.

6. The method for preparing the phosphorescently colored tunable metal-polynitrogen heterocyclic complex glass material according to claim 1, characterized in that, The molar ratio of the polynitrogen heterocyclic ligand to the metal halide is 1-5:

1.

7. The method for preparing the phosphorescently colored tunable metal-polynitrogen heterocyclic complex glass material according to claim 1, characterized in that, The volume ratio of concentrated hydrochloric acid to deionized water is 0.00001-0.1.

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