Syntheses And Properties Of Copper(?) Alkynyl Clusters And Silver Thiolate Clusters Encapsulating POMs

The construction of high-nuclearity coinage metal(Cu,Ag,Au)clusters have been extensively studied for their structural diversity,and intriguing properties in catalysis,optics,and electricity,etc.Metal ions with d10 electron configuration are able to aggregate metal atoms into polynuclear motifs because of the metallophilic interactions.According to HSAB principle(hard and soft acids and bases),because of the affinity of alkyne and sulfide ligands with Cu(?)and Ag(?),they are often used to synthesize ligand-protected copper(?)or silver clusters.To date,there are many huge challenges remained for syntheses of high-nuclearity metal clusters with specific properties:uncontrol of the self-assembly process,methods of synthesizing and characterizing the structure of high quality single crystals.To solve these problems,the anion-templated method has been proved to be an effective way of synthesizing high-nuclearity metal clusters.In this paper,a comproportionation method was used to successfully synthesize 4 copper(?)alkynyl clusters.Also,we used precursors of AgSPhMe-p,adding different kinds of silver salts,POMs anionic templates to obtain different silver thiolate clusters finally.Multiple characterizations were conducted on our products as single-crystal X-ray diffraction(SCXRD)data,elemental analysis,TGA,UV-Vis spectrum and solution behaviors via electrospray mass spectrometry(ESI-MS).The thesis is divided into four parts,which mainly are as following:?:We briefly introduce the overview of metal clusters,and mainly introduce the research progress of the silver thiolate clusters and copper(?)-alkynide cluster.Moreover,we also introduce the synthetic methods of silver sulfide clusters.?:We adopt the comproportionation methodology and four novel copper(?)alkynyl complexes are isolated,[Cuis(tBuC ? C)10(CF3COO)5]·tBuC ? CH(1),[Cu16(tBuC?C)12(CF3COO)4(CH3OH)2](2),[Cu15(tBuC ? C)10(CF3COO)5]·CH3C6H5(3),and[Cu14(tBuC?C)10(CH3COO)4]·CHCl3(4).All of these stable clusters are capped off by tBuC?C-and O atoms from COO-.We also discussed the optical properties and solution behaviors in details.?:We obtained two novel silver thiolate clusters,[Ag12(SPhMe-p)6(CF3COO)6(DMF)6(CH3CN)2](5)and[Mo8O28@Ag48(SPhMe-p)24(CF3COO)14]·2(CF3COO)(6)The complex 6 is a core-shell configuration,which consists of a[Mo8O28]8-anion template and a[Ag48S24]shell.What is more,the optical properties and its solution behaviors are also discussed in details.?:On the basis of the previous chapter,four novel silver clusters(7-10)are synthesized when adding dppm as protected ligands.These silver thiolate clusters with simple structures are atomically precise.This study exemplified that double phosphine ligands can also be used in synthesizing phosphine-protected silver thiolate clusters.Also,it is of great importance in the further research work.