Thermoluminescent color-changing metal nano-material, preparation method and application of thermoluminescent color-changing metal nano-material

Abstract

The invention discloses a metal nano-material, and particularly discloses a thermoluminescent color-changing metal nano-material, a preparation method and application of the thermoluminescent color-changing metal nano-material. Under ultraviolet excitation, the emission intensity of the thermoluminescent color-changing metal nano material shows a remarkable temperature dependence characteristic. The nano fluorescent thermometer can be used as a nano fluorescent thermometer and has wide application in the technical fields of biomedical treatment, environmental monitoring, nano electronics and the like.

Description

Technical Field

[0001] The invention relates to a thermoluminescent color-changing metal nano material, a preparation method and application thereof, and belongs to the technical field of metal nano materials. Background Art

[0002] With the continuous advancement of science and technology, temperature monitoring has become increasingly important in many fields, such as industrial process control, environmental monitoring, medical diagnosis, and bioimaging. However, traditional thermometers usually have defects such as large size, invasive temperature measurement, and slow response speed, which limits their effectiveness in many application scenarios. Therefore, the development of new temperature sensing materials is of great practical significance.

[0003] In recent years, fluorescence temperature measurement technology has attracted widespread attention due to its remote temperature measurement, non-invasiveness, high sensitivity and high spatial resolution. This technology uses the characteristic that the emission intensity of fluorescent materials changes with temperature to achieve non-contact measurement of temperature. Compared with traditional temperature measurement methods, fluorescence thermometers have faster response times and higher measurement accuracy, and are particularly suitable for application scenarios that are sensitive to temperature changes. Among the many temperature-sensitive fluorescent materials, silver cluster nanomaterials in metal nanomaterials have shown good application potential in biomedicine, bioprocess monitoring and biotechnology due to their excellent optical properties, low toxicity and good biocompatibility. Although some nanosilver cluster materials with temperature-dependent fluorescence intensity have been synthesized and reported, the overall number is still limited. Further exploration and development of new silver cluster nanomaterials can not only enrich the material library of fluorescence thermometers, but also promote research and application development in related fields. Summary of the invention

[0004] The technical problem to be solved by the present invention is to provide a novel thermoluminescent color-changing metal nanomaterial; during the temperature change process, the emission intensity at 606nm and 492nm respectively shows good linear and exponential relationships, and the material can be applied to technical fields such as biomedicine, environmental monitoring and nanoelectronics.

[0005] The first object of the present invention is to provide a thermoluminescent color-changing metal nanomaterial, the molecular formula of which is [Ag 36 (Hdecz) 12 (CF3SO3)4(NO3)3(dppm)4](CF3SO3)5;

[0006] The NO3 is a nitrate; the CF3SO3 is a trifluoromethanesulfonate;

[0007] The dppm is bis(diphenylphosphino)methane The Hdecz is

[0008] Preferably, according to the present invention, the above-mentioned thermoluminescent color-changing metal nanomaterial can be prepared by the following method;

[0009] (1) Alkyne silver precursor: Under alkaline conditions, silver (I) salt and 3,6-di-tert-butyl-1,8-diethyl-9H-carbazole undergo polymerization reaction in a solvent to generate an acetylenic silver precursor;

[0010] (2) dissolving the silver acetylene precursor, silver (I) trifluoromethanesulfonate, bis(diphenylphosphine)methane and nitrate in a solvent to prepare the product through a self-assembly reaction;

[0011] Wherein, the structural formula of the 3,6-di-tert-butyl-1,8-diethyl-9H-carbazole is

[0012] Preferably according to the present invention, in step (1), the silver (I) salt may be one or a combination of more than one of Ag2O, AgNO3, AgF, AgCl, AgBr, AgI, CF3SO3Ag, AgClO4, AgBF4, AgPF6 or AgSbF6.

[0013] Preferably, according to the present invention, in step (1), depending on the different silver (I) salts, the polar solvent can be one or a combination of more than one of water, chloroform, dichloromethane, acetonitrile, ethanol or methanol.

[0014] Preferably according to the present invention, in step (1), the base can be one or a combination of more than one of ammonia water, triethylamine, sodium hydroxide, potassium hydroxide, sodium hydride, calcium hydride, sodium methoxide, tetramethylethylenediamine, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, tetrapropylammonium hydroxide, and tetraethylammonium hydroxide.

[0015] Preferably according to the present invention, in step (1), the molar ratio of the silver (I) salt to 3,6-di-tert-butyl-1,8-diethyl-9H-carbazole is 2-2.5:1.

[0016] Preferably according to the present invention, in step (2), the polar solvent may be one or a combination of more than one of dichloromethane, chloroform, acetonitrile, 1,2-dichloroethane, dimethyl sulfoxide, N,N-dimethylformamide, and N,N-dimethylacetamide.

[0017] Preferably according to the present invention, in step (2), the nitrate is one or a combination of more than one of potassium nitrate, sodium nitrate, ammonium nitrate, tetramethylammonium nitrate, tetraethylammonium nitrate, tetrapropylammonium nitrate and tetrabutylammonium nitrate.

[0018] Preferably according to the present invention, in step (2), the reaction ratio of the acetylenic silver precursor, silver (I) trifluoromethanesulfonate, bis(diphenylphosphino)methane and nitrate is 11-13:11-13:3-5:2-4, and the optimal reaction molar ratio is 12:12:4:3.

[0019] The second object of the invention is to provide a method for preparing the above-mentioned thermoluminescent color-changing metal nanomaterial, which can be the method for preparing the above-mentioned thermoluminescent color-changing metal nanomaterial described in this article.

[0020] Invention Objective 3: To provide a crystal form of the above-mentioned thermoluminescent color-changing metal nanomaterial, wherein the unit cell parameters of the crystal form are: α(deg)=90; β(deg)=102.191(3); γ(deg)=90.

[0021] A fourth object of the invention is to provide an application of the above-mentioned thermoluminescent color-changing metal nanomaterial in a molecular fluorescence thermometer.

[0022] At room temperature, when the thermoluminescent color-changing metal nanomaterial is excited by ultraviolet light (λ ex =250nm-500nm) shows orange-red emission. Its maximum emission peak is 600nm, and the maximum emission peak lifetime is 59.8ns. When the temperature drops from 30℃ to -190℃, the maximum emission peak at 600nm gradually redshifts to 606nm. The emission intensity at 606nm shows a linear growth relationship with temperature. In addition, when the temperature drops, a new emission peak appears at 492nm, and its emission intensity shows an exponential growth relationship with temperature.

[0023] It can be seen that the above-mentioned silver metal nanomaterials can be used as the core material of nano-fluorescence thermometers.

[0024] Without violating the common sense in the art, the above-mentioned preferred conditions can be arbitrarily combined to obtain the preferred embodiments of the present invention.

[0025] Unless otherwise specified, the reagents and raw materials used in the present invention are commercially available.

[0026] The technical features and beneficial effects of the present invention are as follows:

[0027] The 3,6-di-tert-butyl-1,8-diethyl-9H-carbazole ligand used in the thermoluminescent color-changing metal nanomaterial of the present invention has a variety of deprotonation modes, and each acetylene group also exhibits a rich coordination mode, which enables the nanocluster to assemble into silver nanoclusters with diverse topological structures and rich luminescence properties.

[0028] The preparation method disclosed in the present invention is simple and mild, and the post-treatment process is relatively simple, which meets the needs of industrial production.

[0029] The nanoclusters exhibit significant temperature-dependent emission characteristics over a wide temperature range, specifically from 30°C to -190°C. At 606nm and 492nm, the emission intensity shows good linear and exponential relationships with temperature changes, respectively. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 This is a single crystal structure diagram of thermoluminescent color-changing metal nanomaterials. For simplicity, all hydrogen atoms, the tert-butyl group on 3,6-di-tert-butyl-1,8-diethyl-9H-carbazole, and the benzene ring on bis(diphenylphosphino)methane are omitted.

[0031] Figure 2 The excitation of thermoluminescent metal nanomaterials in the solid state (λ em = 600nm, dotted line) and emission (λ ex =365nm, solid line) curve.

[0032] Figure 3 is the maximum emission peak of thermoluminescent color-changing metal nanomaterials in the solid state (λ max =600nm) lifetime decay curve.

[0033] Figure 4 This is the temperature-dependent fluorescence curve of the thermoluminescent color-changing metal nanomaterial in the solid state, with an excitation wavelength of 365nm.

[0034] Figure 5 The graph shows the variation of the emission intensity of the solid-state thermoluminescent color-changing metal nanomaterial at λ=606nm with temperature.

[0035] Figure 6 The graph shows the variation of the emission intensity of the solid-state thermoluminescent color-changing metal nanomaterial at λ=492nm with temperature. DETAILED DESCRIPTION

[0036] In order to make the purpose, technical scheme and technical effect of the present invention clearer, the present invention is further described in detail below with reference to the accompanying drawings and examples; however, the present invention is not limited to the described examples. The experimental methods in the following examples without specifying specific conditions shall be selected according to conventional methods and conditions, or according to the product instructions.

[0037] The 3,6-di-tert-butyl-1,8-diethyl-9H-carbazole involved in the present invention is prepared according to Dalton Trans. 2017, 46, 4696-4710, and other reagents and solvents can be obtained commercially.

[0038] Example 1: Synthesis method of thermoluminescent color-changing metal nanomaterials in the present invention

[0039] (1) Weigh 1 equivalent of silver oxide and add it to 25% ammonia water, stir until it is clear, and obtain a silver ammonia solution. Dissolve 1 equivalent of 3,6-di-tert-butyl-1,8-diethyl-9H-carbazole in 1,4-dioxane and add it dropwise to the silver ammonia solution under vigorous stirring. The reaction quickly generates a red precipitate, and the stirring is continued for 6 hours. Then filter, wash with water 3 times, and vacuum dry the water to obtain a red silver acetylene precursor with a yield of 82.7%.

[0040] (2) 12 equivalents of acetylene silver precursor, 12 equivalents of silver (I) trifluoromethanesulfonate, 4 equivalents of bis(diphenylphosphine)methane and 3 equivalents of ammonium nitrate were dissolved in dichloromethane and stirred at room temperature for 12 hours to obtain a deep red solution. The mother liquor was transferred to a test tube, 3 volumes of n-hexane were spread on it for interfacial diffusion, and the tube was sealed and allowed to stand for 5 days to obtain a red block-shaped thermoluminescent color-changing metal nanomaterial crystal with a crystal yield of 80.5%.

[0041] Example 2: Synthesis method of thermoluminescent color-changing metal nanomaterials in the present invention

[0042] (1) Weigh 2 equivalents of silver nitrate, dissolve it in water, and add ammonia water with a mass concentration of 25% dropwise. The system first generates a gray precipitate, which then slowly dissolves. When the system becomes clear again, stop adding drops to obtain a silver ammonia solution. Dissolve 1 equivalent of 3,6-di-tert-butyl-1,8-diethyl-9H-carbazole in 1,4-dioxane and add it dropwise to the silver ammonia solution under vigorous stirring. The reaction quickly generates a red precipitate and continues stirring for 6 hours. Then filter, wash with water 3 times, and vacuum dry the water to obtain a red silver acetylene precursor with a yield of 83.5%.

[0043] (2) 12 equivalents of acetylene silver precursor, 12 equivalents of silver (I) trifluoromethanesulfonate, 4 equivalents of bis(diphenylphosphine)methane and 3 equivalents of tetrabutylammonium nitrate were dissolved in chloroform and stirred at room temperature for 12 hours to obtain a deep red solution. The reaction mother liquor was left to evaporate for one week in the dark to obtain red flaky thermoluminescent color-changing metal nanomaterial crystals with a crystal yield of 82.5%.

[0044] Example 3: Synthesis method of thermoluminescent color-changing metal nanomaterials in the present invention

[0045] (1) Weigh 2 equivalents of silver nitrate and add them to a methanol solution containing 1 equivalent of 3,6-di-tert-butyl-1,8-diethyl-9H-carbazole. Add 10 equivalents of triethylamine dropwise under vigorous stirring, and the reaction quickly generates a large amount of red precipitate. Continue stirring for 6 hours until all the white silver nitrate crystals disappear. Then filter, wash with methanol 3 times, and vacuum-drain the methanol to obtain a red silver acetylene precursor with a yield of 70.6%.

[0046] (2) 12 equivalents of silver acetylene precursor, 12 equivalents of silver (I) trifluoromethanesulfonate, 4 equivalents of bis(diphenylphosphine)methane and 3 equivalents of potassium nitrate were dissolved in N,N-dimethylacetamide and stirred at room temperature for 12 hours to obtain a deep red solution. The mother liquor was transferred to a test tube, 3 volumes of ether were spread on it for interfacial diffusion, and the tube was sealed and allowed to stand for 7 days to obtain red block-shaped thermoluminescent color-changing metal nanomaterial crystals with a crystal yield of 40.5%.

[0047] Example 4: Synthesis method of thermoluminescent color-changing metal nanomaterials in the present invention

[0048] (1) Weigh 2 equivalents of silver (I) trifluoromethanesulfonate (0.2 mmol) and 1 equivalent of 3,6-di-tert-butyl-1,8-diethyl-9H-carbazole, add dichloromethane, and sonicate to dissolve all reactants. Add 10 equivalents of triethylamine dropwise to the system, and the reaction solution changes from light yellow to dark red. Continue stirring for 6 hours. Remove all dichloromethane and excess triethylamine. Wash with methanol 3 times, filter, and vacuum dry the methanol to obtain a red silver acetylene precursor with a yield of 77.8%.

[0049] (2) 12 equivalents of silver acetylene precursor, 12 equivalents of silver (I) trifluoromethanesulfonate, 4 equivalents of bis(diphenylphosphine)methane and 3 equivalents of potassium nitrate were dissolved in dichloromethane and stirred at room temperature for 12 hours to obtain a deep red solution. The mother liquor was transferred to a test tube, 3 volumes of n-hexane were spread on it for interfacial diffusion, and the tube was sealed and allowed to stand for 5 days to obtain red block-shaped thermoluminescent color-changing metal nanomaterial crystals with a crystal yield of 35.8%.

[0050] Example 5: Synthesis method of thermoluminescent color-changing metal nanomaterials in the present invention

[0051] (1) Weigh 1 equivalent of 3,6-di-tert-butyl-1,8-diethyl-9H-carbazole and 2 equivalents of sodium hydroxide, add methanol, and sonicate until all the sodium hydroxide is dissolved. Then add 2 equivalents of AgBF4, and a large amount of red precipitate is quickly produced. Continue stirring for 6 hours. Filter, wash with methanol 3 times, and vacuum dry the methanol to obtain a red silver acetylene precursor with a yield of 80.1%.

[0052] (2) 12 equivalents of silver acetylene precursor, 12 equivalents of silver (I) trifluoromethanesulfonate, 4 equivalents of bis(diphenylphosphine)methane and 3 equivalents of ammonium nitrate were dissolved in dichloromethane and stirred at room temperature for 12 hours to obtain a deep red solution. The mother liquor was transferred to a test tube, 3 volumes of n-hexane were spread on it for interfacial diffusion, and the tube was sealed and allowed to stand for 5 days to obtain red block-shaped thermoluminescent color-changing metal nanomaterial crystals with a crystal yield of 18.5%.

[0053] Example 6: Structural Characterization

[0054] The crystal obtained in Example 1 was used as an example to characterize the single crystal structure. The X-ray single crystal diffraction data of the crystal was collected on a Bruker DiffractometerMD2 diffractometer at the BL17B beamline of the National Center for Protein Science (NCPSS) in Shanghai. The data was processed using the Bruker APEX4 program. The wavelength of the light source is The test temperature is 273K. The crystal is of triclinic Cc space group. The unit cell volume is 46077(8). Ag 26 The molecular formula of the cluster is C 397 H 364 Ag 36 F 27 N 15 O 36 P8S9. Its molecular weight is 10853.89. Other crystal related information is shown in Table 1:

[0055] Table 1

[0056]

[0057] Ag 36 The single crystal structure of silver nanoclusters is shown in Figure 1 As shown, its molecular formula [Ag 36 (Hdecz) 12 (CF3SO3)4(NO3)3(dpp

[0058] m)4](CF3SO3)5. The core of the silver cluster is composed of thirty-six silver atoms, and the shell is composed of twelve deprotonated 3,6-di-tert-butyl-1,8-diethyl-9H-carbazole, four trifluoromethanesulfonate, three nitrate and four bis(diphenylphosphino)methane, with the counter ion being trifluoromethanesulfonate. During the coordination process, 3,6-di-tert-butyl-1,8-diethyl-9H-carbazole coordinates with silver atoms by removing hydrogen from the bilateral ethynyl groups, forming a variety of coordination modes, including: (1) μ3-η 1 :η 1 :η 1 ,μ3-η 1 :η 1 :η 1 (2) μ3-η 2 :η 1 :η 1 ,μ3-η 1 :η 1 :η 1 (3)μ3-η 2 :η 1 :η 1 ,μ3-η 2 :η2 :η 1 (4)μ4-n2:n1:n1:n1,μ4-n2:n1:n1:n1 (5)μ4-n1:n1:n1:n1,μ4-n2:n1:n1:n1 The nitrate ions are divided into two groups, two of which are coordinated to one silver atom through Ag-O bonds. The other uses a bidentate coordination mode to bridge three silver atoms. One oxygen atom of the trifluoromethanesulfonate group coordinates with one silver atom through an Ag-O bond. Bis(diphenylphosphino)methane, as a bidentate ligand, bridges two silver atoms through an Ag-P bond.

[0059] Example 7: Photophysical testing

[0060] In the present invention, the thermoluminescent color-changing properties of the material have been studied in depth. The excitation and emission spectra and emission lifetime in the present invention are characterized by Edinburgh Analytical Instruments (FLS920 fluorescence spectrometer). At room temperature, when the metal nanomaterial is excited by ultraviolet light with a wavelength of 250nm to 500nm, it exhibits orange-red fluorescence emission, and its maximum emission peak is located at 600nm ( Figure 2 ), the fluorescence lifetime is 59.8ns( Figure 3 As the temperature decreases from 30°C to -190°C, the emission peak at 600nm gradually red-shifts to 606nm ( Figure 4 ). At the same time, the emission intensity at 606nm shows a linear relationship with temperature ( Figure 5 ). In addition, as the temperature decreases, a new emission peak appears at 492nm, and its emission intensity shows an exponential growth relationship with temperature ( Figure 6 ).

Claims

1. A thermoluminescent color-changing metal nanomaterial, whose molecular formula is [Ag 36 (Hdecz) 12 (CF3SO3)4(NO3)3(dppm)4](CF3SO3)5; The NO3 is a nitrate; the CF3SO3 is a trifluoromethanesulfonate; The dppm is bis(diphenylphosphino)methane The Hdecz is 2. The thermoluminescent color-changing metal nanomaterial according to claim 1, characterized in that: The thermoluminescent color-changing metal nanomaterial is prepared by the following method: (1) Under alkaline conditions, silver (I) salt and 3,6-di-tert-butyl-1,8-diethyl-9H-carbazole undergo polymerization reaction in a solvent to generate an acetylene silver precursor; (2) dissolving the silver acetylene precursor, silver (I) trifluoromethanesulfonate, bis(diphenylphosphine)methane and nitrate in a solvent, and preparing the thermoluminescent color-changing metal nanomaterial through a self-assembly reaction; Wherein, the structural formula of the 3,6-di-tert-butyl-1,8-diethyl-9H-carbazole is 3. The thermoluminescent color-changing metal nanomaterial according to claim 2, characterized in that: In step (1), the silver (I) salt is one or a combination of more than one of Ag2O, AgNO3, AgF, AgCl, AgBr, AgI, CF3SO3Ag, AgClO4, AgBF4, AgPF6 or AgSbF6.

4. The thermoluminescent color-changing metal nanomaterial according to claim 2, characterized in that: In step (1), the solvent is one or a combination of more than one of water, chloroform, dichloromethane, acetonitrile, ethanol or methanol.

5. The thermoluminescent color-changing metal nanomaterial according to claim 2, characterized in that: In step (1), the base is one or a combination of more than one of ammonia water, triethylamine, sodium hydroxide, potassium hydroxide, sodium hydride, calcium hydride, sodium methoxide, tetramethylethylenediamine, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, tetrapropylammonium hydroxide, and tetraethylammonium hydroxide.

6. The thermoluminescent color-changing metal nanomaterial according to claim 2, characterized in that: In step (1), the molar ratio of the silver (I) salt to 3,6-di-tert-butyl-1,8-diethyl-9H-carbazole is 2-2.5:

1.

7. The silver metal nanomaterial according to claim 2, characterized in that: In step (2), the nitrate is one or a combination of more than one of potassium nitrate, sodium nitrate, ammonium nitrate, tetramethylammonium nitrate, tetraethylammonium nitrate, tetrapropylammonium nitrate and tetrabutylammonium nitrate.

8. The thermoluminescent color-changing metal nanomaterial according to claim 2, characterized in that: In step (2), the solvent is one or a combination of dichloromethane, chloroform, acetonitrile, 1,2-dichloroethane, dimethyl sulfoxide, N,N-dimethylformamide, and N,N-dimethylacetamide; And / or, in step (2), the reaction ratio of the acetylenic silver precursor, silver (I) trifluoromethanesulfonate, bis(diphenylphosphino)methane and nitrate is 11-13:11-13:3-5:2-4, and the optimal reaction molar ratio is 12:12:4:

3.

9. A crystal form of the thermoluminescent color-changing metal nanomaterial according to any one of claims 1 to 8, characterized in that: Unit cell parameters of the crystal form: α(deg)=90; β(deg)=102.191(3); γ(deg)=90.

10. Use of the thermoluminescent color-changing metal nanomaterial according to any one of claims 1 to 8 in a ratio fluorescence thermometer.

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