Study Of The Preparation And Properties Of High-nucleus Silver Alkynyl Clusters Templated By Octahedral Tellurate Ions

High-nucleus silver clusters have attracted extensive attention from researchers due to their diverse structures and potential applications.However,the preparation process of Ag clusters is complicated,and their formation involves the orderly assembly of multiple components.As most silver clusters have excellent optical properties,the research on how to improve their properties by the regulation of their structures is extremely important.Early research shows using silver alkynyl as the precursor to react with soluble silver salts can prepare a series of high-nuclear silver alkynyl clusters with novel structures and different properties,under the assistant of anion templates and the second ligands,and by adjusting pH,by changing solvents,etc.With new advances in research on the structure of silver clusters,scientists are gradually turning their attention to the surface structure modification and performance improvements of the high-nucleus silver alkynyl clusters.Therefore,in this paper,the negative hexavalent octahedral tellurate is used as the anion template to synthesize a high-nucleus alkynyl silver cluster,and its decomposition process was analyzed with mass spectrometry.The method of surface coordination substitution is used to guide the construction of its derivatives,and then the structure-activity relationships between their structures and optical properties are studied based on the differentiation of their surface structures.The research in this article mainly includes the following three parts:(1)A 36-core alkynyl silver cluster,named(TeO6)@Ag36(C?CtBu)18(tfa)12(1),was constructed by using tellurate as template anion.And by introducing pentafluorobenzoic acid into the reaction system,the ligands on the surface of the cluster were successfully replaced.An isomorphic 36-core silver alkynyl cluster,named(TeO6)@Ag36(C?CtBu)18(tfa)8(F5PhCO2)4(2),was obtained.Their preparation process and their formation conditions are mainly discussed.(2)Through X-ray single crystal diffraction analysis,combined with infrared spectroscopy(FT-IR),X-ray powder diffraction(PXRD),electrospray mass spectrometry(ESI-MS),X-ray photoelectron spectroscopy(XPS)and other characterization methods,the structures of both clusters are accurately characterized.Their crystal structures are described in detail.(3)The thermal stability,solid-state light absorption and photoluminescence properties of the two clusters were compared and studied.The research results show that both clusters have good thermal stability,similar solid-state light absorption capacity and significant fluorescence difference.The discussion is centred on the variation of their fluorescence properties caused by the differences in their surface structures.