Structure Regulation And Properties Of Anion Templated High-nuclearity Silver Clusters

High-nuclearity silver clusters have attracted great attention from chemists owing to their beautiful structures and various properties.However,their synthesis is always awe-inspiring and represents an extraordinary level of sophistication in the coordination assembly system due to the flexible coordination preferences of Ag(?)ions and the coexisting coordination bond and argentophilic interaction.The effectiveness of anion templates in the construction of high-nuclearity silver clusters has been witnessed.In this thesis,we combined POM with other simple anions to form hetero-anion templated sliver cluster,isolated anisotropic silver clusters through combining anion templates and mixed ligands we employed a strategy combining anion templates and solvent functionalities to assemble core-shell silver clusters with different inner core.All compounds have been determined by single-crystal X-ray crystallography,UV-Vis spectra,IR,flurescence spectroscopy and etc.This thesis consists of four parts:?:We briefly introduce the research progress,synthesis methods and properties of silver thiolate clusters.?:We synthesized and characterized two unprecedented mixed ligands coprotected nanoclusters,(HNEt3)10[(MoO4)5@Ag52S6(tBuC6H4S)20(dppm)10(MoO4)10](1)and[(Mo6O22)2@Ag76(MeOC6H4S)28(dppm)8(MoO4)16(H2O)8·8CH3OH·4CH3CN](2),they are interiorly templated by five MoO42-and a pair of bicubane M06O228-anions,respectively.Regiospecific distribution of diphosphine ligands on the surface and the arrangement of multiple molybdate templates within the nanoclusters synergetically tailor their shapes to anisotropic oblate spheroid and elongated rod,respectively.This work not only enriches the anisotropic silver clusters but also give important insights for the anisotropic growth of silver nanoclusters through surface modifications or/and template organizations.?:we developed a hetero-anion template method to assemble a giant Ag90 cluster,[(SO4)2(W5O19)2@Ag90(tBuC6H4S)44(PhCOO)24(DMF)2(H2O)2]·2PhCOO(3),which was identified as a dumbbell-like neutral molecule trapping paired W5O198-and SO42-anions in the head and waist sections,respectively.Both W5O198-and SO42-templates were in situ generated and synergistically induced the formation of the largest known anion-templated silver cluster.To the best of our knowledge,this is the first W5O198-built from face-shared W4O4 cubane and W3O3 opened cubane.The formation of such a giant silver cluster is proven to be collaboratively regulated by two types of anion templates.The solution stability,optical properties and temperature-dependent emission behaviors of this cluster were also discussed in detail.?:We successfully employed a strategy combining anion templates and solvent functionalities to assemble three-shell Ag70 nanoclusters--one formed as dark-red crystals in the presence of reductive DMF with an inner Agio kernel,surrounded by a ring of seven MoO42-ions and enveloped by a shell of 60 Ag atoms,and the other obtained as yellow crystals in the absence of DMF with an inner core of five MoO42-ions,4 Ag atoms,and 4 S2-ions,wrapped by 66 Ag atoms.The novel Ag10 kernel is built from five Ag4 tetrahedra that share edges or faces.This work not only provides a new Ag4 tetrahedron fusion growth mode but also gives important prospects for the capture of elusive embryonic silver species by using anion templates in the hierarchical multi-shell silver nanocluster assembly process.