Method for selectively preparing gold cluster polycrystalline phase based on halogenation engineering

Abstract

The invention discloses a method for selectively preparing a gold cluster polycrystalline phase based on halogenation engineering, and belongs to the crossing field of coordination chemistry and material science. The crystal structure of the Au4 cluster is regulated and controlled through a ligand halogenation engineering strategy. The R / Sau4-H cluster before halogenation only has one crystal structure, and after the ligand is modified by a halogenation engineering strategy, weak interaction among molecules can be selectively activated by controlling the types of solvents, so that the polycrystalline phase structure of the cluster is accurately regulated and controlled. F atoms are introduced, so that two polycrystalline phase cluster enantiomers R / Sau4-F and (R / Sau4-F) 4 can be obtained; three kinds of polycrystalline phase cluster enantiomers, namely R / Sau4-Cl, (R / Sau4-Cl) 3 and (R / Sau4-Cl) n, can be obtained by introducing Cl atoms; two polycrystalline phase cluster enantiomers R / Sau4-Br and (R / Sau4-Br) 3 can be obtained by introducing Br atoms. The synthesis of the gold cluster polycrystal phase can be selectively controlled, and the accurate regulation and control of the crystal phase structure are realized.

Description

Technical Field

[0001] This invention belongs to the interdisciplinary field of coordination chemistry and materials science, and relates to a method for selectively preparing Au4 cluster polycrystalline compounds based on an efficient halogenation engineering strategy. Background Technology

[0002] Atomic-sized metal clusters, due to their unique quantum size effect and the modifiability of their surface ligands, have shown great promise in fields such as photoelectrocatalysis and molecular sensing. Currently, cluster research faces the following challenges: (1) High-yield preparation of clusters: Clusters tend to aggregate during preparation, resulting in complex products and thus low yields of single clusters. (2) Controllable construction of cluster structures: Due to the diverse surface structures of clusters, their controllable construction is difficult. (3) High stability and high activity of clusters: For example, the mutual coupling between the internal forces of clusters leads to a very limited response to external interventions.

[0003] In recent years, the development of weak intermolecular interactions such as halogen bonds and halo-halogen interactions has provided new ideas for the controllable synthesis of coin metal clusters. Halogen atoms (F, Cl, Br) can regulate cluster growth through the following mechanisms due to their high electronegativity and diverse non-covalent interaction modes: (1) By synergistically regulating the electron cloud distribution of ligands on the periphery of the cluster through inductive and conjugation effects, the electronic structure and reactivity of the cluster are significantly affected. (2) By selectively stabilizing specific crystal planes through steric hindrance effects, the orientation of growth can be controlled. (3) Since most halogen atoms can act as both hydrogen bond acceptors and halogen bond donors, the introduction of halogen atoms can significantly expand the types of non-covalent interactions between clusters.

[0004] The above highlights the unique advantages of halogenation engineering strategies in single-crystal phase synthesis, but their application potential in the construction of multi-crystal phase systems has not yet been fully explored. Summary of the Invention

[0005] To effectively address the key technical challenges of polycrystalline phase mixing and precise control of atomic-level structure in the current synthesis of coin metal clusters, this invention specifically designs and develops a halogenation engineering strategy that can effectively drive and precisely control the polycrystalline phase synthesis of Au4 clusters.

[0006] The specific technical solution is as follows: The chemical formula of the Au4 cluster is C 36 H 28 Au4N4S8, named R / S Au4-H. This cluster is represented by (S / R)-4-phenylthiazolidin-2-thione (abbreviated as: R / S Ph-H) is the protective ligand.

[0007] The halogenation strategy proposed in this invention refers to... R / S In the Ph-H synthesis, the starting material (R / S)-2-amino-2-phenylethanol is replaced with (R / S)-2-amino-2-(4-halophenyl)ethanol. Based on the original synthesis, the synthetic route is optimized to prepare a series of (R / S)-4-(4-halophenyl)thiazolidin-2-thiones (abbreviated as: R / S Ph-X), where the halogen atom (X) can be F, Cl, or Br. The specific synthetic routes before and after the implementation of the halogenation strategy are shown in the figure below: Will contain respectively R Ph-X or S A solution of Ph-X (X = F, Cl, Br) and gold sulfide is mixed, and triethylamine is added. By adjusting the solvent, weak intermolecular interactions can be selectively activated. Due to the size differences of F, Cl, and Br atoms and the corresponding differences in the types and strengths of intermolecular forces, Au4-X clusters are induced to assemble into polycrystalline compounds. Following the above method... R / S Ph-F ligands can be obtained R / S Au4-F and ( R / S Enantiomers of two polycrystalline phase clusters with different structures, Au4-F4; R / S Ph-Cl ligands can be obtained R / S Au4-Cl, ( R / S Au4-Cl)3 and ( R / S Au4-Cl) n Three enantiomers of polycrystalline phase clusters with different structures; R / S Ph-Br ligands can be obtained R / S Au4-Br and ( R / S Au4-Br)3 is an enantiomer of two polycrystalline phase clusters with different structures.

[0008] The regulating solvent is selected from dichloromethane, methanol, acetone, and acetonitrile.

[0009] The beneficial effects of this invention are: (1) A halogenation strategy was successfully designed to drive the controllable synthesis of Au4 cluster polycrystalline phases, realizing precise control of crystal phase structure; (2) Atom-level precise polycrystalline phase control technology was developed, and the "ligand-structure" synergistic design principle was established, providing a universally applicable design idea for the rational design of high-performance cluster-based functional materials. Attached Figure Description

[0010] Figure 1 Before halogenation in this invention R / SA schematic diagram of the enantiomeric structure of the Au4-H cluster. The color codes in the diagram are: golden yellow for Au, dark gray for C, orange for S, and blue for N. The H atom is omitted for clarity.

[0011] Figure 2 For the present invention R / S Au4-F and ( R / S Two polycrystalline phase cluster enantiomers with different structures (Au4-F)4 are shown in the figure. The color codes are: golden yellow for Au, dark gray for C, orange yellow for S, blue for N, and light green for F. H atoms are omitted for clarity of structure.

[0012] Figure 3 For the present invention R / S Au4-F and ( R / S XRD pattern of Au4-F)4 cluster.

[0013] Figure 4 For the present invention R / S Au4-Cl, ( R / S Au4-Cl)3 and ( R / S Au4-Cl) n The three polycrystalline phase cluster enantiomers with different structures are shown in the figure. The color codes are: golden yellow for Au, dark gray for C, orange yellow for S, blue for N, and green for Cl. H atoms are omitted for clarity of structure.

[0014] Figure 5 For the present invention R / S Au4-Cl, ( R / S Au4-Cl)3 and ( R / S Au4-Cl) n XRD pattern of the cluster.

[0015] Figure 6 For the present invention R / S Au4-Br and ( R / S Two polycrystalline phase cluster enantiomers with different structures of Au4-Br)3 are shown in the figure. The color codes are: golden yellow for Au, dark gray for C, orange yellow for S, blue for N, and yellowish brown for Br. H atoms are omitted for clarity of structure.

[0016] Figure 7 For the present invention R / S Au4-Br and ( R / S XRD pattern of Au4-Br)3 cluster. Detailed Implementation

[0017] To better illustrate the present invention, the following embodiments are provided:

Example 1

[0018]

Example 2

[0019] (4.26 mg 0.02 mmol) R Ph-F or S Ph-F was dissolved in 1 mL of acetonitrile, and (6 mg 0.02 mmol) of Me2SAuCl was dissolved in 3 mL of dichloromethane. The two solutions were mixed thoroughly, and then 10 μL of triethylamine was added. After standing for 48 hours to evaporate, block crystals suitable for testing were formed.

[0020]

Example 3

[0021] Will R Ph-Cl or SPh -Cl (4.60 mg, 0.02 mmol) was dissolved in 1 mL of acetonitrile, and Me2SAuCl (6 mg, 0.02 mmol) was dissolved in 3 mL of acetone. After thoroughly mixing the two solutions, 10 μL of triethylamine was added. After the mixture was allowed to stand for 8 hours, flaky crystals that met the testing requirements precipitated.

[0022] 900 μL 1 mmol / L R Au4-Cl or S The Au4-Cl solution in N,N-dimethylformamide was transferred to a centrifuge tube, followed by the addition of 100 μL of deionized water. After the mixture was allowed to stand for 24 hours, needle-like crystals that met the testing requirements precipitated.

[0023]

Example 4

[0024] (5.46 mg, 0.02 mmol) R Ph-Br or S Ph-Br was dissolved in 1 mL of dichloromethane, and (6 mg, 0.02 mmol) Me₂SAuCl was dissolved in 1 mL of acetone. The two solutions were thoroughly mixed, and then 10 μL of triethylamine was added. After standing for 30 minutes, flaky crystals meeting the testing requirements precipitated.

[0025]

Example 5

[0027] The above embodiments are only used to illustrate the content of this invention. Other embodiments of this invention are also possible. However, all technical solutions formed by equivalent substitution or equivalent modification fall within the protection scope of this invention.

Claims

1. A method for preparing a gold cluster polymorph phase, characterized by, The method is as follows: (1) in an alkaline solution, using R-2-amino-2-(4-halophenyl)ethanol or S-2-amino-2-(4-halophenyl)ethanol as raw material, adding carbon disulfide, heating and stirring to react; after the reaction is completed, the mixture is cooled to room temperature, the reaction solution is extracted and dried to obtain a crude product; the crude product is purified to obtain a series of (R / S)-4-(4-halophenyl)thiazolidine-2-thione, which is abbreviated as R / SPh-X, X represents F, Cl, Br; (2) dissolving RPh-X or SPh-X and sulfur ether gold in a control solvent respectively, mixing the solutions, then adding triethylamine to obtain a gold cluster polycrystalline phase enantiomer; The control solvent in step (2) is selected from dichloromethane, methanol, acetone and acetonitrile.

2. The method for preparing the polycrystalline phase of gold clusters as described in claim 1, characterized in that, The gold cluster polycrystalline phase enantiomer is R / SAu4-F and (R / SAu4-F)4 two polycrystalline phase cluster enantiomers with different structures; R / SAu4-Cl, (R / SAu4-Cl)3 and (R / SAu4-Cl)n three polycrystalline phase cluster enantiomers with different structures; R / SAu4-Br and (R / SAu4-Br)3 two polycrystalline phase cluster enantiomers with different structures.

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