Synthesis And Properties Of Organic Acid Participated Silver(?) Thiolate Clusters And Mixed-Valenced Silver Thiolate Clusters

The construction of high-nuclearity silver(?)clusters is an active frontier in contemporary chemistry in view of their structural diversity and wide application.On the hand,studying on the regulation of silver cluster structure by anionic templates have been matured,but the studing on the effect of the outer organic ligands on the structure of silver clusters is still in the preliminary stage.On the other hand,although a series of high-nuclear silver nanoclusters have been reported,the embryo states of silver nanoparticles are quite difficult to be captured due to their typical kinetics-controlled growth course,thus,it is of great significance to control the reductive transformation from Ag(?)to Ag(0).In this work,based on[tBuSAg]n and[CyhSAg]n precursor,seven silver(?)/thiolate compounds were synthesized by introducing benzoic acid,phenylphosphonic acid ligands and empolying the solvent regulation strategy.The structures and properties of these complexes were characterized by X-ray single crystal diffractometer,Infrared Spectra,UV-Vis,Luminescence and Electrospray Ionization Mass Spectrometry(ESI-MS).The thesis consists of four sections:?:The research process of silver clusters.?:Carboxylic acid-induced high-nuclearity silver thiolate clusters.We used[tBuSAg]n precursor,anion template and different carboxylic acid ligand synthesized three silver clusters:(nBu4NH)[(Ag3S3)@Ag29(tBuS)16(PhCOO)9(MoO4)(H2O)·CH3OH](1),[(?-MO5O18)@Ag38(tBuS)18(PhCOO)14·2CH2Cl2](2)and[(Ag21S13)@Ag57(tBuS)28(MeOPhCOO)14(MoO4)5·CH3CN](3).Note that the Zang group has reported a very similar silver cluster Ag33,after careful comparison of 1 and Ag33,the major difference lies in their metallic shells,1 has one less Ag atom than Ag33.This is seemingly a slight difference,but it has a great influence on the structure.These important findings clearly prove the significant role of carboxylates in shaping the silver thiolate clusters.The three new clusters emit luminescence in the near-infrared(NIR)region and show different thermochromic luminescence properties.?:Core-shell structured silver clusters capped by thiolate/phenylphosphonate.With the low-temperature solvothermal method and[tBuSAg]n as precursor,we abtained two core-shell structure silver clusters and a one-dimensional(1D)coordination polymer by introducing phenylphosphonic acid:{(H30)7[Ag45S5(tBuS)24(PPA)9]}(4),{[Ag66S6(tBuS)24(PPA)12(HPPA)2(CN)4]n}(5)and {(H30)11[Ag73S14(tBuS)32(PPA)12]}(6).The low-temperature solvothermal reaction promoted the in situ decomposition of tBuSH to produce S2+ ions,in addition to in situ C-S bond breaking,the formation of polymeric 5 also involves CN bridges derived from acetonitrile by C-C bond cleavage.The solution behaviors and optical absorption properties of the three nests are described in detail.Of note,4 and 6 emit in the near-infrared region and show different luminescent thermochromic behavior.?:.fcc-structured Agio kernels silver cluster Ag80.We used a DMF containing mixed solvent system to isolate a nove three-shell silver nanocluster:[Ag10@(Mo7O26)2@Ag7O(MoO4)2(CyhS)36(CF3SO3)16(DMF)6]·2DMF·4nPrOH(7).The fcc-structured Ag10 kernel is built from two single-edge opened Ag6 octahedra by sharing one edge and further locked by a pair of Mo7O2610-anions to form an inner Ag10@(Mo7O26)2 core which is finally encapsulated by an outer Ag70 shell to form three-shell Ag10@(Mo7O26)22@Ag70 nanoclusters.Notably,the bioctahedral Ag10 kernel has not been observed in silver nanocluster ever before,the bioctahedral Ag10 core can be deemed as a brand-new embryo state of silver nanoparticles.Crescent-like Mo7O2610-anion have not been observed in POM chemistry ever before.Then we studied the luminescence character.