Syntheses And Properties Of Multi-Anion Templated Silver Alkynyl Clusters And Diphosphine-Protected Gold Clusters

High-nuclearity silver clusters have attracted much attention due to their structural diversities and various potential applications.The synthesis of these compounds often involves the orderly combination of several components(metal centers and a variety of ligands),and most of the silver compounds are easily decomposed by light.Therefore,it is of great challenge to improve their stability.Previous studies showed that choose the protective acetylene silver as precursor,by changing the anionic templates,counteracting anions,pH and solvent,we can synthesize a series of novel high-nuclearity silver compounds.In this work,based on[tBuC?CAg]n?[PhC-=CAg]n?[cPrC?CAg]n precursor,by changing the anion template,soluble silver salt and types of ligand for synthesis of a series of silver alkynyl clusters,and study the various factors that affect their structures.The structure and properties of these complexes were characterized by X-ray single crystal diffractometer,Elemental Analysis,Electrospray Ionization Mass Spectrometry(ESI-MS),Infrared Spectra,Luminescence,UV-Vis and Thermogravimetry.The thesis consists of four sections:I:The research process and synthesis methods of silver clusters.II:Multi-Anion Templated Nanosized Silver Alkynyl Clusters.With the solvothermal method and[tBuC?CAg]n as precursor,we abtained two hetero anion silver alkynyl clusters by changing soluble silver salt:{[(CrO4)2Cl@Ag42(PhC=C)34(CF3COO)2]·CF3COO}(1),{(NH4)[(CrO4)2Cl@Ag42(PhC?C)34(CrO4)(H2O)2]·2BF4·CH3OH}n(2)and two homo anions silver alkynyl clusters:{[(CrO4)@Ag22(PhC?C)16(CF3SO3)4·2CH3OH·H2O}n(3),{[(CrO4)2@Ag31(PhC?C)22(CF3SO3)4]·CF3SO3·2CH3OH·H2O}n(4).Crystals of 1-4 were dissolved in solvent and the solution behaviors were investigated using electrospray ionization mass spectrometry.After carefully matching experimental mass spectra with calculated isotope distributions,we can assigned the peaks to the species of Ag42,Ag22,Ag40.When changing polyoxometallates(POMs)as anion template,we have obtained the largest polyoxometalate-templated silver-alkynyl clusters known.[(EuW10O36)2@Ag72(tBuC?C)48Cl2·4BF4](5).Then we studied the ESI-MS behavior and luminescence character.?:A Water-Stable Cluster Based Metal-Organic Open Framework.In this work,we use[cPrC?CAg]n as precursor to synthesize a Cl@Ag14 cluster based metal-organic open framework:[Cl@Ag]4(cPrC?C)10Cl2·(p-TOS)·1/3H2O]n(6).We sought to use such a water-stable cationic framework to investigate the exchange of anion between p-TOS and Cr2O72-,then render it as promising prototype adsorbent of Cr? from wastewater.We run the reaction in other non-chlorinated solvents such as CH3(CH2)3OH,the one-dimensional silver-alkynyl coordination polymer,[Ag16(cPrC?C)8(p-TOS)8(CH3(CH2)3OH)2-2(CH3(CH2)3OH)]n(7)was obtained.IV:Diphosphine-Protected Ultrasmall Gold Nanoclusters:Opened Icosahedral Au13 and Heart-Shaped Au8 Clusters.We use Au2(dppm)2Cl2 as precusour and under the action of reducing agent obtained an open icosahedral Au13 and heart-shaped Au8 clusters.The common Au13 cluster is an ideal icosahedron,which has the symmetry of Ih,and what we get is a C3 symmetric structure.Through the analysis of single crystal structure,three Au-Au distances were much longer than those observed in many other phosphine-protected Au nanoclusters,while the other Au8 cluster was the structure type of "core + 4exo" that was not reported previously.The understanding of their electronic structure is also obtained through quantum chemical calculation.What is interesting is that the Au8 clusters show the phenomenon of thermofluorescence discoloration,which is not seen in the gold clusters.This study thus not only enriches the structures of ultrasmall gold nanoclusters but also provides fundamental insights into their electronic structures and luminescent properties.