Synthesis,Structure And Properties Of Silver Cluster Compounds Constructed By Tert-butyl Alkyne Silver Ligands

Transition metal alkynyl complexes are widely used in nonlinear optical materials,fluorescent materials and rigid molecular materials due to their excellent coordination ability,high stability and strong?electron binding ability.Under the action of metallophiles in the metal center of Group IB?copper,silver and gold?coins,ethynyl groups with multiple coordination patterns react with them to form clusters,aromatic rings and long-chain clusters.Among them,high-nuclear silver cluster compounds have attracted much attention due to their beautiful structure and potential application value.Although it has been reported that a variety of high-nuclear silver clusters with beautiful structures have been synthesized,due to their low yields and stability and strict requirements on experimental conditions,most of their current research is only on the structural level And there is very little exploration of their deeper nature.Since its synthetic route is self-assembled and cannot be controlled,the artificially directed design of synthetic high-core silver clusters is a persistent challenge in this field.In this paper,a simple organic ligand?silver tert-butylacetylene?is used,and then some soluble auxiliary ligands?silver trifluoroacetate,silver trifluoromethanesulfonate?are added to change the reaction ratio and the solvent.For different species,a series of high-nuclear silver clusters with different configurations were synthesized using different synthesis methods?normal temperature stirring,solvothermal method?.The prepared crystals were characterized by X-ray powder diffraction spectrum analysis,infrared spectrum analysis,thermogravimetric analysis,and ultraviolet spectrum analysis,and then their structures were determined,and their optical and electrical properties were studied.The main work of this article is as follows:1.We used Ag[C?C^tBu]_n as the main ligand and CF₃COOAg as the auxiliary ligand.Under solvothermal conditions,we synthesized a high-yield1D chain silver acetylene cluster[Ag₈?C?C^tBu?₅?CF₃COO?₃?CH₃CN?]_n?1?.In this work,we described its synthesis method and crystal structure,and studied its luminescence and electrochemical properties.2.We used a conventional stirring method to synthesize a high-nuclear silver cluster constructed with VO₃^–as an anion template.Each unit cell of the compoundcontainstwodifferentmonomerclusters?A?[Ag₂₄?VO₃?₂?C?C^tBu?₁₂?CF₃SO₃?₆,?B?[Ag₂₄?VO₃?₂?C?C^tBu?₁₄?CF₃SO₃?₆?2?,compound 2 has been proved to be a thermally stable material,and the compound 2 has very good luminescence properties.3.We synthesized a 28-core silver acetylene cluster Ag₂₈?Mo O₄?₂?Bu^tC?C?₁₈?CF₃COO?₆?3?with tetrahedral Mo O₄^2–as an anion template.In this reaction,the template anion Mo O₄^2–source For the conversion of polyacid Na₅[Cu PMo₁₁O₃₉].n H₂O.We introduced the synthesis method and crystal structure of cluster compound 3,and further understood the importance of using anions as templates in the synthesis of high-nuclear silver clusters.