Study On The Synthesis,Structure And Properties Of High Nuclear Mercaptan Silver Clusters

High-nuclear thiol silver clusters are a class of excellent inorganic metal sulfides,monovalent metal ions with d¹⁰ electronic structure.Because of its beautiful structure and diversity of properties,it is becoming more and more important in the fields of synthesis,catalysis,materials,biology,medicine,etc.,and it has received extensive attention from chemists.Although the high-nuclear silver thiol cluster can be synthesized by a simple method,it still requires tedious and repeated experiments after preparation,and the high-nuclear silver thiol cluster has limited its development due to its low yield and low stability.At present,many explorations of high-nuclear thiol silver clusters are still at the structural level.How to design and synthesize a specific high-nuclear thiol silver cluster is still a huge challenge.In order to achieve a controllable structure and function,we tried many different assembly strategies and different auxiliary ligands to change the synthesis conditions of high-nuclear silver thiol clusters.Anionic templates also play a crucial role in the construction of high-nuclear thiol silver clusters.Different template anions are used to combine different soluble solvents and soluble ligands to form high-nuclear thiol silver clusters with different structures.In the text,we have successfully synthesized several silver clusters with higher nuclear degrees through several excellent synthesis strategies,including self-assembly methods,anionic template methods,geometric polyhedra,and LEIST?size/structure transformation caused by ligand exchange?.The main work is divided into the following three our parts:?1?:Wesynthesizedtheclustercompound[Ag₃₁S₃?S^tBu?₁₇?CF₃COO?₇?CO₃?_0.5?CF₃COOH?_0.5?DMF?₄]·3DMF·CH₃OH?referred to as Compound 1?by one-pot method with AgS^tBu and CF₃COOAg).Compound 1 has been proven to have thermal and chemical stability,and also exhibits temperature-sensitive light-emitting characteristics.Choosing DMF as the solvent for the initial synthesis,DMF has a mild reducing ability,which can make the silver cluster compound grow slowly,and the crystallization process of the cluster compound is easier to be observed.The results show that DMF also acts as a ligand to participate in the framework coordination.?2?:We used Na[CuPMo₁₁O₃₉]·n H₂O as the source of Mo and Mo O₄^2-as the anion template to obtain the spherical cage-like structure Compound 2 by one-pot synthesis.It has been confirmed that Compound 2 is chemically stable in solution at room temperature.Through this work,we introduced the synthesis method and crystal structure of the cluster compound Compound 2,and further understood the importance of using anions as templates in the synthesis of high-nuclear silver thiol clusters.?3?:We used AgS^tBu ligand and isopropyl alcohol auxiliary ligand to self-assemble in a solution of DMF:CH₂Cl₂:isopropyl alcohol?1:1:1?,and obtained a case of high-nuclear silver thiol cluster Ag₁₀₄S₇?S^tBu?₂₇?ⁱPr?₂?Referred to as compound 3?.In this cluster compound,Ag₃ is used as the core of the cluster compound,and Ag-S bonds are alternately linked to form a high-nuclear silver thiol cluster cluster.