Preparation method of near-infrared luminous AgPd super-atomic cluster and application of near-infrared luminous AgPd super-atomic cluster in 3D printing

Abstract

The invention relates to a preparation method of a near-infrared luminous AgPd super-atomic cluster and application of the near-infrared luminous AgPd super-atomic cluster in 3D printing, and belongs to the crossing field of coordination chemistry and nano materials. The chemical formula of the AgPd super-atomic cluster is C216H150Ag14F30P10PdS6 (abbreviated as Ag14Pd), the AgPd super-atomic cluster belongs to a hexagonal crystal system, and the space group is a chiral space group R3 () c. The cluster has strong near-infrared luminescence at room temperature, wherein the optimal emission wavelength in a solid state is 780 nm; the optimal emission wavelength in a solution state is 768nm; the maximum light-emitting quantum yield in a solid state reaches up to 15%. In addition, the super-atomic cluster also shows excellent thermal stability. The cluster has high optical activity and solubility at room temperature, can be used as ink for 3D printing to print macroscopic models of various shapes and sizes, and shows that the near-infrared luminous cluster material has potential application prospects in photoelectric devices.

Description

Technical Field

[0001] The present invention belongs to the cross-field of coordination chemistry and nanomaterials, and relates to a preparation method of a near-infrared luminescent AgPd superatomic cluster and its application in 3D printing. Background Art

[0002] Atomically precise coin metal (gold, silver, copper) clusters are a type of cluster with atomically precise structure, with an outer layer protected by organic ligands and an inner core composed of three or more coin metal atoms through metal-philic interactions. Nanoclusters are a state of matter between atoms and bulk materials, and are a bridge between atoms and macroscopic matter. They are generally nanoscale in size and are often accompanied by quantum confinement effects, which produce many new phenomena and properties. Their excellent photophysical properties and their potential applications in catalysis, bioimaging, and other fields have become a research hotspot in materials and inorganic chemistry in recent years.

[0003] Nanoclusters have excellent optical properties, good photostability and good biocompatibility, which make them have a wide range of application prospects. At present, the research on coin metal nanoclusters is mainly focused on the synthesis of new nanoclusters, but the coin metal nanoclusters reported so far mainly emit light in the visible light wavelength region (such as blue light, yellow light, red light, etc.) under room temperature conditions, and the luminescence quantum efficiency is low. These defects have greatly hindered the application and development of nanoclusters, so designing and synthesizing nanoclusters with precise atoms, near-infrared luminescence and high luminescence efficiency is one of the current research focuses.

[0004] At present, the research on coin metal nanoclusters mainly focuses on the synthesis of new clusters, while the exploration of their applications is still scarce. The excellent luminescence performance of clusters has potential application prospects in the fields of light-emitting diodes, information storage, and display. Therefore, it is urgent to develop the application exploration of metal clusters with high luminescence efficiency. Summary of the invention

[0005] The present invention aims to provide a method for preparing a near-infrared luminescent AgPd superatomic cluster. Another object is to provide an application of the near-infrared luminescent AgPd superatomic cluster in 3D printing.

[0006] In order to achieve the above object, the present invention provides the following technical solutions: A near-infrared luminescent AgPd superatomic cluster with the chemical formula C 216 H 150 Ag 14 F 30 P 10 PdS6 (abbreviated as: Ag 14 Pd), belongs to the hexagonal system, and the space group is a chiral space group R 3(_) c , Ag14 Pd: a =21.0082(1)Å, b =21.0082(1)Å, c =88.3377(5)Å, α =90°, β =90°(10), γ =120°, V =33764.0(4)Å 3 .

[0007] The method for preparing the near-infrared luminescent AgPd superatomic cluster comprises the following steps: First, silver nitrate and tetrakis(triphenylphosphine)palladium are dissolved in a solvent mixture of methanol and dichloromethane at room temperature. Then, pentafluorothiophenol and triphenylphosphine are added to the above mixture under vigorous stirring to form a Pd-Ag-SP complex. Subsequently, a freshly prepared sodium borohydride aqueous solution is added to the above reaction solution, and the reaction mixture is aged for five hours. Subsequently, the aqueous phase is removed and a n-hexane solution is added. After about two days, red-black rhombus block crystals are obtained, which are filtered, washed with n-hexane, and dried at room temperature.

[0008] The near-infrared luminescent AgPd superatomic cluster has an icosahedral Ag 12 The Pd core has two silver atoms covering two triangular Ag3 faces along the three-fold axis of the icosahedron. 12 The triangular faces of the Pd icosahedron form two opposing tetrahedral geometries, with each edge of the tetrahedral waist bridged by a pentafluorothiophenol ligand. Eight triphenylphosphine ligands surround the two silver atoms at the ends and the six silver atoms arranged in a chair cyclohexane conformation at the icosahedral waist.

[0009] Furthermore, the properties of the near-infrared luminescent AgPd superatomic cluster are specifically described as follows: The material has strong near-infrared luminescence at room temperature, with the best emission wavelength in the solid state being 780nm (the best excitation wavelength being 590nm) ( Figure 2 As shown); the optimal emission wavelength in solution is 768nm (optimal excitation wavelength 560nm) ( Figure 3 Its maximum luminescence quantum yield in the solid state is as high as 15%, which is rare among the reported superatomic clusters. In addition, the superatomic cluster exhibits excellent thermal stability when continuously irradiated with 400nm light for three hours ( Figure 4 The cluster has strong optical activity and solubility at room temperature, which makes it have good application prospects. It can be used as ink in 3D printing to print macro models of various shapes and sizes ( Figure 5As shown in the figure, the model was applied to optoelectronic devices, indicating that near-infrared luminescent cluster materials have potential application prospects in optoelectronic devices.

[0010] The beneficial effects of the present invention are: The AgPd superatomic cluster material shown in the present invention is a type of scarce near-infrared luminescent material. It not only has bright near-infrared luminescence at room temperature, but also has an optimal emission wavelength of 780nm and a quantum yield of up to 15%. The superatomic cluster also exhibits excellent thermal stability. The cluster has strong near-infrared optical activity and solubility at room temperature, can be used as an ink component for 3D printing, and is used for 3D printing macro models, and has good application prospects.

[0011] The above description is only an overview of the technical solution of the present invention. In order to more clearly understand the technical means of the present invention and implement it according to the contents of the specification, the following is a detailed description of the preferred embodiments of the present invention in conjunction with the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0012] Figure 1 It is a schematic diagram of the structure of the AgPd superatomic cluster material of the present invention.

[0013] Figure 2 This is an excitation emission curve diagram of the AgPd superatomic cluster material of the present invention in a solid state.

[0014] Figure 3 It is an excitation emission curve diagram of the AgPd superatomic cluster material of the present invention in the solution state.

[0015] Figure 4 This is a photostability diagram of the maximum emission wavelength of the AgPd superatomic cluster material of the present invention changing with time.

[0016] Figure 5 This is a macroscopic model diagram of the AgPd superatomic cluster material of the present invention used as ink through 3D printing. DETAILED DESCRIPTION

[0017] The technical solution of the present invention will be described clearly and completely below in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0018] In addition, the technical features involved in the different embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other. Example 1

[0019] Chiral ligand R / S -NHCpy -H·PF6 (0.5mmol, 275mg) and excess copper powder (1.5mmol, 96mg) were stirred in acetonitrile for 24 hours. The suspension was filtered and reduced to 2mL, and 50mL of ether was added to obtain a white crude product powder. The white powder was dissolved in 1mL of acetonitrile and diffused with ether to obtain colorless crystals. 10mg of AgNO3 and 5mg of Pd(TPP)4 were dissolved in a mixture of methanol (2mL) and dichloromethane (4mL) at room temperature and stirred for 5min, and then 10µL of pentafluorothiophenol and 50mg of triphenylphosphine were added.

[0020] Then, 1 ml of NaBH4 aqueous solution (10 mg / mL) was quickly added to the reaction mixture under vigorous stirring. The color of the solution immediately changed from a yellow solution to a red solution. Then the reaction was continued in the dark at room temperature for 5 hours. Then the aqueous phase was removed. The organic phase was rinsed with water several times. After 2 days, red rhombus single crystals suitable for X-ray diffraction research were cultivated in n-hexane / CH2Cl2 solution, filtered, washed with n-hexane, and dried at room temperature to obtain AgPd superatomic clusters. Example 2

[0021] The AgPd superatomic cluster material prepared in Example 1 was further characterized as follows: (1) Crystal structure determination The X-ray single crystal diffraction data of the complex were measured on a Rigaku XtaLAB Pro single crystal diffractometer using a single crystal sample of appropriate size. The data were collected at 200K by ω scanning using graphite monochromatized CuKα rays (λ=1.54184Å) as the diffraction source, and were corrected by Lp factor and semi-empirical absorption. The structure was first solved by the direct method using the SHELXS-97 program, and then refined using the full matrix least squares method using the SHELXL-97 program. All non-hydrogen atoms were refined using the anisotropic thermal parameter method. All hydrogen atoms were refined using the isotropic thermal parameter method. Detailed crystal measurement data are shown in Table 1.

[0022]

[0023] R 1=∑׀׀ F o ׀-׀ F c ׀׀ / ∑׀ F o ׀. wxya 2=[∑ w ( F o 2 - F c2 ) 2 / ∑ w ( F o 2 ) 2 ] 1 / 2 The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0024] The above-mentioned embodiments only express several implementation methods of the present invention, and the description thereof is relatively specific and detailed, but it cannot be understood as limiting the scope of the invention patent. It should be pointed out that for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, which all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be based on the attached claims.

Claims

1. A near-infrared luminescent AgPd superatomic cluster, characterized in that: The chemical formula of the AgPd superatomic cluster is: 216 H 150 Ag 14 F 30 P 10 PdS6 (abbreviated as: Ag 14 Pd), belongs to the hexagonal system, and the space group is a chiral space group R 3(_) c , Ag 14 Pd: a =21.0082(1)Å, b =21.0082(1)Å, c =88.3377(5)Å, α =90°, β =90°(10), γ =120°, V =33764.0(4)Å 3 .

2. The near-infrared luminescent AgPd superatomic cluster according to claim 1, characterized in that: With an icosahedral Ag 12 Pd core, in which two silver atoms cover two triangular Ag3 faces along the three-fold axis of the icosahedron, and the two silver atoms are 12 The triangular faces of the Pd icosahedron form two opposing tetrahedral geometries, in which each edge of the tetrahedral waist is bridged by a pentafluorothiophenol ligand, and eight triphenylphosphine ligands surround the two silver atoms at the two ends and the six silver atoms arranged in a chair cyclohexane conformation at the icosahedral waist.

3. The use of the near-infrared luminescent AgPd superatomic cluster in 3D printing according to any one of claims 1 to 2, characterized in that: It is used as ink in 3D printing to print macro models, which are then used in optoelectronic devices.

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