Preparation and application of an organic-inorganic heterometallic halide

Abstract

The present invention discloses an organic-inorganic heterometallic halide and its preparation and application. Specifically, anhydrous piperazine, ammonium salt, metal salt and hydrochloric acid solution are added to a polytetrafluoroethylene-lined high-pressure reactor, and the general formula C is obtained by program temperature control. 20 H 67 N 12 X 3Cl 20 Materials ( X By regulating the ratio of metal salts and ammonium salts, different luminescent materials can be obtained. These materials, due to their excellent luminescence performance and novel photophysical properties, have great application potential in many cutting-edge fields such as trace methanol detection, light-emitting diodes, and optical information anti-counterfeiting.

Description

Technical Field

[0001] The present invention belongs to the field of material technology, and specifically relates to an organic-inorganic heterometallic halide, a preparation method thereof, and an application thereof in the field of luminescence. Background Art

[0002] Zero-dimensional organic-inorganic heterometallic halides are a class of crystalline materials with a unique "host-guest" structure. Their diverse crystal structures and rich luminescence physical properties make them show great application potential in the optoelectronic field. On the one hand, this type of material has excellent optical properties, such as adjustable luminescence color and extremely high luminescence efficiency, making it a potential candidate for optoelectronic device materials. On the other hand, due to its ionic characteristics and low formation energy, it can undergo reversible transformation under different external environmental stimuli, making it expected to be used as an optical solid-state switch to explore its application in gas sensing, energy storage, information encryption, etc. However, in current research, there are few reports on the development of multifunctional organic-inorganic heterometallic halide materials. Summary of the Invention

[0003] The purpose of the present invention is to provide an organic-inorganic heterometallic halide and its preparation and application. By regulating the ratio of metal salts and ammonium salts, different luminescent materials can be obtained. These materials have great application potential in many cutting-edge fields such as trace methanol detection, light-emitting diodes, and optical information anti-counterfeiting due to their excellent luminescence performance and novel photophysical properties.

[0004] To achieve the above object, the present invention adopts the following technical solutions:

[0005] A method for preparing an organic-inorganic heterometallic halide comprises adding anhydrous piperazine, an ammonium salt, a metal salt and a hydrochloric acid solution into a polytetrafluoroethylene-lined autoclave, setting the initial temperature at 20-40°C, then heating to 80-115°C, reacting at a constant temperature for 50-72 hours, and finally cooling to 20-30°C to obtain an organic-inorganic heterometallic halide C. 20 H 67 N 12 X 3Cl 20 ,in, X One or more metallic elements.

[0006] Furthermore, the ammonium salt is ammonium carbonate or ammonia water.

[0007] Furthermore, the metal salt is a halide, oxide or hydroxide of a rare metal.

[0008] Furthermore, the concentration of the hydrochloric acid solution is 10-12 mol / L, and the amount thereof is added at 1-6 mL per millimole of anhydrous piperazine.

[0009] Specifically, the chemical formula of the obtained organic-inorganic heterometallic halide is C 20 H 67 N 12 Sb3Cl 20 or C 20 H 67 N 12 In 1.13 Sb 1.87 Cl 20 , which are all orthorhombic structures, and the space group is Pbam .

[0010] Furthermore, when the prepared heterometallic halide is C 20 H 67 N 12 Sb3Cl 20 When the metal salt used is trivalent antimony salt, the molar ratio of anhydrous piperazine, ammonium salt and trivalent antimony salt is 1:0.05~0.5:1~0.5. When the prepared heterometallic halide is C 20 H 67 N 12 In 1.13 Sb 1.87 Cl 20 When the metal salts used are trivalent antimony salt and trivalent indium salt, the molar ratio of anhydrous piperazine, ammonium salt, trivalent antimony salt and trivalent indium salt is 1:0.05~0.5:1~0.5:0.125~6.

[0011] The trivalent antimony salt used may specifically be antimony trioxide, antimony hydroxide, or antimony trichloride, and the trivalent indium salt used may specifically be indium trichloride, indium trichloride tetrahydrate, indium chloride polyhydrate, indium oxide, indium hydroxide, and the like.

[0012] Income C 20 H 67 N 12 Sb3Cl 20 The crystal can emit orange-yellow light, with International Commission on Illumination coordinates of (0.5111, 0.4576), a color temperature of 2331 K, an emission peak at 617 nm, and a quantum yield of 19%; the obtained C 20 H 67 N 12 In 1.13 Sb 1.87 Cl 20 The crystal can emit strong yellow light, with International Commission on Illumination coordinates of (0.4873, 0.4807), a color temperature of 2764 K, an emission peak at 595 nm, and a quantum yield of 100%. Therefore, it can be used in luminous fields such as light-emitting diodes or optical information anti-counterfeiting.

[0013] At the same time, the prepared C 20 H67 N 12 In 1.13 Sb 1.87 Cl 20 Under methanol induction (direct or indirect contact with methanol gas or methanol liquid), the crystal can obtain C9H 28 N4OIn 0.38 Sb 0.62 Cl7 crystal, International Commission on Illumination coordinates are (0.4002, 0.4986), color temperature is 4210 K, emission peak is at 553 nm, quantum yield can be up to 67%, its crystal is orthorhombic structure, space group is Pbca. 28 N4OIn 0.38 Sb 0.62 Cl7 crystals can be combined with C 20 H 67 N 12 In 1.13 Sb 1.87 Cl 20 The crystal undergoes a reversible structural transition, accompanied by a fluorescence change from strong yellow light to strong green light, and can therefore be used to detect trace amounts of methanol; its operating temperature range is 0°C~120°C, and the visual methanol detection limit is less than 20 ppm.

[0014] The advantages of the present invention are:

[0015] (1) The present invention can prepare organic and inorganic heterometallic halide materials with high luminous efficiency in one step. The synthesis method is simple and reproducible, the required raw materials are abundant in source, and the target crystals obtained are of good quality and stability.

[0016] (2) In the process of preparing the organic-inorganic heterometallic halide material according to the present invention, the photophysical properties such as fluorescence quantum yield, decay lifetime, and emission wavelength can be controlled by simply adjusting the ratio of metal elements to ammonium salts. As a result, this type of material, which has been developed for the first time, can be applied in trace methanol detection (a detection limit of 20 ppm can be obtained at an operating temperature of 120°C), light-emitting diodes (lumen efficiency of approximately 139 lm / W, color rendering index of approximately 86), and optical information anti-counterfeiting. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 C in the present invention 20 H 67 N 12 Sb3Cl 20 Crystal, C 20 H 67 N 12 In 1.13 Sb 1.87 Cl 20Crystal and C9H 28 N4OIn 0.38 Sb 0.62 Schematic diagram of the transformation of Cl7 crystals.

[0018] Figure 2 C prepared in Example 1 20 H 67 N 12 Sb3Cl 20 Powder X-ray diffraction pattern of crystals.

[0019] Figure 3 C prepared in Example 1 20 H 67 N 12 Sb3Cl 20 Orange-yellow emission spectrum of the crystal under 388 nm laser excitation.

[0020] Figure 4 C prepared in Example 2 20 H 67 N 12 In 1.13 Sb 1.87 Cl 20 Powder X-ray diffraction pattern of crystals.

[0021] Figure 5 C prepared in Example 2 20 H 67 N 12 In 1.13 Sb 1.87 Cl 20 Yellow emission spectrum of the crystal under 383 nm laser excitation.

[0022] Figure 6 C9H prepared in Example 3 28 N4OIn 0.38 Sb 0.62 Green emission spectrum of Cl7 crystal under 340 nm laser excitation.

[0023] Figure 7 C 20 H 67 N 12 In 1.13 Sb 1.87 Cl 20 Crystal and C9H 28 N4OIn 0.38 Sb 0.62 Graph showing the changes in luminescence intensity during the reversible cyclic conversion of Cl7 crystals.

[0024] Figure 8 C 20H 67 N 12 In 1.13 Sb 1.87 Cl 20 A diagram showing the use of crystals for visual detection of trace amounts of methanol.

[0025] Figure 9 For C-based 20 H 67 N 12 In 1.13 Sb 1.87 Cl 20 Emission spectrum of the white light-emitting diode prepared by the crystal under 383 nm violet light excitation.

[0026] Figure 10 For C-based 20 H 67 N 12 In 1.13 Sb 1.87 Cl 20 Image of flexible light-emitting film sample prepared by crystal. DETAILED DESCRIPTION

[0027] In order to make the contents of the present invention easier to understand, the technical solutions of the present invention are further described below in conjunction with specific implementation methods, but the present invention is not limited thereto.

[0028] Example 1C 20 H 67 N 12 Sb3Cl 20 Crystal synthesis

[0029] In a 28.0 mL polytetrafluoroethylene-lined reactor, 1.0 mmol of anhydrous piperazine, 0.25 mmol of ammonium carbonate, 1.0 mmol of antimony trichloride, and 6 mL of 10 mol / L hydrochloric acid solution were added. The initial temperature was set at 20°C, then the temperature was raised to 100°C at a rate of 0.53°C / min, held constant for 3000 min, and then cooled to 25°C at a rate of 0.054°C / min. C was obtained by filtration. 20 H 67 N 12 Sb3Cl 20 crystal.

[0030] Figure 2 Prepared C 20 H 67 N 12 Sb3Cl 20 Powder X-ray diffraction pattern of crystals.

[0031] Figure 3 Prepared C20 H 67 N 12 Sb3Cl 20 The orange-yellow emission spectrum of the crystal under 388 nm laser excitation. As shown in the figure, the prepared material can emit orange-yellow light under 388 nm laser excitation. The emission peak is at 617 nm, with International Commission on Illumination coordinates of (0.5111, 0.4576), a color temperature of 2331 K, and a quantum yield of 19%.

[0032] Example 2C 20 H 67 N 12 In 1.13 Sb 1.87 Cl 20 Crystal synthesis

[0033] In a 28.0 mL polytetrafluoroethylene-lined reactor, 1.0 mmol of anhydrous piperazine, 0.25 mmol of ammonium carbonate, 0.375 mmol of indium oxide, 0.5 mmol of antimony trioxide, and 3 mL of 10 mol / L hydrochloric acid solution were added. The initial temperature was set at 25 °C, then the temperature was raised to 97 °C at a rate of 0.6 °C / min, held constant for 2400 min, and then cooled to 25 °C at a rate of 0.03 °C / min. C was obtained by filtration. 20 H 67 N 12 In 1.13 Sb 1.87 Cl 20 crystal.

[0034] Figure 4 Prepared C 20 H 67 N 12 In 1.13 Sb 1.87 Cl 20 Powder X-ray diffraction pattern of crystals.

[0035] Figure 5 Prepared C 20 H 67 N 12 In 1.13 Sb 1.87 Cl 20 Yellow emission spectrum of the crystal under 383 nm laser excitation. As shown in the figure, the prepared material exhibits strong yellow emission under 383 nm laser excitation. The emission peak is at 595 nm, with International Commission on Illumination coordinates of (0.4873, 0.4807), a color temperature of 2764 K, and a quantum yield of 100%.

[0036] Example 3C9H 28 N4OIn 0.38 Sb 0.62 Synthesis of Cl7 crystals

[0037] 30 mg of C prepared in Example 2 was added 20 H 67 N 12 In 1.13 Sb 1.87 Cl 20 The crystals were contacted with 1.5 mL of methanol (gas / liquid) in a small glass vial for 5 minutes to obtain C9H 28 N4OIn 0.38 Sb 0.62 Cl7 crystals.

[0038] Figure 6 Prepared C9H 28 N4OIn 0.38 Sb 0.62 Green emission spectrum of Cl7 crystal under 340 nm laser excitation. As shown in the figure, the prepared material exhibits strong green emission under 340 nm laser excitation. The emission peak is located at 553 nm, with International Commission on Illumination coordinates of (0.4002, 0.4986), a color temperature of 4210 K, and a quantum yield of 67%.

[0039] The obtained C9H 28 N4OIn 0.38 Sb 0.62 Cl7 crystals can release methanol under external stimulation (temperature, pressure, etc.), thereby achieving structural transformation and producing fluorescence changes. Figure 7 C 20 H 67 N 12 In 1.13 Sb 1.87 Cl 20 Crystal and C9H 28 N4OIn 0.38 Sb 0.62 A graph showing the luminescence intensity changes of a Cl7 crystal after at least five reversible transformations during heating and cooling cycles.

[0040] Figure 8 C 20 H 67 N 12 In 1.13 Sb 1.87 Cl 20 The luminescence of the crystal under the condition of a methanol / ethanol volume ratio of 0.002% and after heating, as well as the corresponding emission spectrum changes, are shown in the figure. As shown in the figure, it can be used for the visual detection of trace methanol.

[0041] Example 4 Based on C 20 H 67 N 12 In 1.13 Sb 1.87 Cl 20 Preparation of Crystalline White Light Emitting Diodes

[0042] C 20 H 67 N 12 In 1.13 Sb 1.87 Cl 20 Crystals and commercial phosphors (BaMgAl 10 O 17 :Eu 2+ (BAM)) were fully mixed in a mass ratio of 1:10, and an appropriate amount of polysiloxane was added as a matrix and mixed thoroughly. The mixture was then coated on a UV LED chip to produce a white light-emitting diode.

[0043] Figure 9 For C-based 20 H 67 N 12 In 1.13 Sb 1.87 Cl 20 The emission spectrum of a white light-emitting diode fabricated from a crystal under 383 nm ultraviolet light excitation. As can be seen from the figure, the display index of the fabricated white light-emitting diode is approximately 90.

[0044] Example 5 Based on C 20 H 67 N 12 In 1.13 Sb 1.87 Cl 20 Preparation of Crystalline White Light Emitting Diodes

[0045] C 20 H 67 N 12 In 1.13 Sb 1.87 Cl 20 The crystals and polydimethylsiloxane were fully and evenly mixed in a mass ratio of 1:150, and then coated and dried to prepare a flexible light-emitting film.

[0046] Figure 10 For C-based 20 H 67 N 12 In 1.13 Sb 1.87 Cl 20A sample of the crystal's flexible light-emitting film emits bright yellow light when excited by 365nm ultraviolet light.

[0047] The above description is only a preferred embodiment of the present invention. All equivalent changes and modifications made according to the scope of the patent application of the present invention should fall within the scope of the present invention.

Claims

1. A method for preparing an organic-inorganic heterometallic halide, characterized in that: Anhydrous piperazine, ammonium salt, metal salt and hydrochloric acid solution were added to a polytetrafluoroethylene-lined autoclave. The initial temperature was set at 20-40 °C, then the temperature was raised to 80-115 °C, and the reaction was carried out at a constant temperature for 50-72 h. Finally, the temperature was lowered to 20-30 °C to obtain heterometallic halide C. 20 H 67 N 12 Sb3Cl 20 or C 20 H 67 N 12 In 1.13 Sb 1.87 Cl 20 ; Among them, the preparation of C 20 H 67 N 12 Sb3Cl 20 When the metal salt used is a trivalent antimony salt, the molar ratio of anhydrous piperazine, ammonium salt and trivalent antimony salt is 1:0.05~0.5:1~0.5; preparation C 20 H 67 N 12 In 1.13 Sb 1.87 Cl 20 When the metal salts used are trivalent antimony salt and trivalent indium salt, the molar ratio of anhydrous piperazine, ammonium salt, trivalent antimony salt and trivalent indium salt used is 1:0.05~0.5:1~0.5:0.125~6.

2. The method for preparing an organic-inorganic heterometallic halide according to claim 1, wherein: The ammonium salt is ammonium carbonate.

3. The method for preparing an organic-inorganic heterometallic halide according to claim 1, wherein: The trivalent antimony salt is antimony trioxide; the trivalent indium salt is indium trichloride.

4. The method for preparing the organic-inorganic heterometallic halide according to claim 3, wherein: The antimony trioxide can also be replaced by antimony hydroxide or antimony trichloride; the indium trichloride can be replaced by indium oxide or indium hydroxide.

5. The method for preparing the organic-inorganic heterometallic halide according to claim 1, wherein The concentration of the hydrochloric acid solution is 10-12 mol / L, and the amount thereof is added at 1-6 mL per millimole of anhydrous piperazine.

6. The method for preparing an organic-inorganic heterometallic halide according to claim 1, wherein: The heterometallic halide has an orthorhombic structure and the space group is Pbam .

7. An organic or inorganic heterometallic halide prepared by the method according to any one of claims 1 to 6.

8. Use of the organic-inorganic heterometallic halide according to claim 7 in the field of luminescence.

9. Use of the organic-inorganic heterometallic halide according to claim 7 in the detection of trace methanol, characterized in that: Heterometallic Halide C 20 H 67 N 12 In 1.13 Sb 1.87 Cl 20 The crystal can be induced by methanol to obtain C9H 28 N4OIn 0.38 Sb 0.62 Cl7 crystals, and both structures are reversible, accompanied by fluorescence changes, so they can be used for trace detection of methanol; its detection limit is less than 20 ppm.

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