Synthesis,Structures,Properties Of High-nuclearity Silver Clusters And Silver Cluster-based Polymer

In recent years,metal nanoclusters with precise structure have become the hotspot in the field of inorganic chemistry,material chemistry and physical chemistry.Among them,high-nuclearity silver nanocluster has been widely concerned by worldwide researchers because of its charming structure and excellent photophysical properties.Most of the current research is tangled at the structural level,without paying much attention in exploring the intrinsic nature and potential properties.Besides,compared with single metal ions,cluster-based MOFs with multinuclear metal clusters as building blocks are easier to construct and assemble the nodes,thus controlling the structure of target materials and obtaining the designed properties.Therefore,it is highly favored by the researchers.At present,metal clusters-based MOFs are mainly focused on metal-oxygen clusters,such as transition metals and a small number of Zr?Ti?-oxygen clusters.The reports relating silver cluster MOFs are currently very limited.In this paper,three high-nuclearity alkynyl-based silver clusters and a series of clusterbased MOFs building with hydrosulphonyl silver nanocluster as secondary building unit are discussed,and their structures and properties are studied.In the first chapter,the characteristics and existing problems of metal clusters and metal cluster-based MOFs are briefly introduced,and their development course is summarized.Meanwhile,some novel high-nuclearity silver clusters with attractive structure and fluorescence performance and flexible coordination polymers with excellent application prospects are discussed.In the second chapter,three stable alkynyl silver clusters were obtained by using tert-butyl phosphoric acid,tert-butylnynal silver and silver trifluoroacetate,[Ag33?CF₃COO?₇?tBuPO₃?4?tBuC?C?14?OH?₃?DMF?3]?CF₃COO?1?,[Ag45?CF₃COO?₇?tBuPO₃?₈?tBuC?C?15?Br?₃?DMF?₃]?2?,[Ag63?P?₂?CF₃COO?₈?tBuPO₃?₉?tBuC?C?19?PO₄?4]?3?.Compound 2 is a mixed-valance silver nanocluster.Compound 3 bears novel structure and excellent fluorescence properties.In the third chapter,two silver cluster MOFs were obtained by using tert-butyl thiolate ligand,phenyl phosphoric acid and bpy as starting materials,{[Ag10?StBu?₆?CF₃COO?₂?PhPO₃H?2?bpy?₂?CH₃CN?₂]}n?4?,{[Ag10?StBu?₆?CF₃COO?₂?PhPO₃H?₂?bpy?₄?xSolvents?]}n?5?.Combined with the characteristics of each structure,we have done a systematic study of the performance of these structures.Compounds 4 and 5 have excellent fluorescence properties and fluorescent response to a variety of volatile organic solvents?VOCs?,which are mainly shown in the way that fluorescent color of the compounds changes under different solvent vapor pressure.In addition,the fluorescence spectra,X-ray powder diffraction and vapor adsorption of compound 5 at different vapor pressures of chloroform were tested and analyzed,and the response mechanism was studied.In the fourth chapter,a three-dimensional structure obtained by using a tridentate nitrogen-containing ligand L₁,{[?Ag10?StBu?₆?CF₃COO?₄?L₁?₆?]?xDMAC]}n?6?,which is a typical rigid skeleton and double interpenetrated structure.It is stable after the removal of the guest molecule.The temperature-dependent fluorescence spectra were tested and the corresponding temperature-sensitive fluorescence photos were photographed.The results showed that from 83 K to 303 K,the fluorescence changed from yellow to yellow-green.