Synthesis And Properties Of Silver(â… ) Thiolate Clusters

Recently, silver chalcogenide clusters attract special attentions of many chemists not only because of their variable and fascinating structures, but their wide variety of properties such as luninescence and conductivity as new materials. Due to the huge difficulties in assembly, growth of high-quality single crystals, X-ray structural solution and characterizations, only limited high-nuclearity silver clusters have been synthesized. Anion templation was proven to be another effective method to achieve the high-nuclearity silver alkynyl clusters by Mak, Wang, Jansen, Vilar and many others groups. In this thesis, we choose 4-tert-Butylthiophenol, 2-Methyl-l-propanethiol and isopropyl mercaptan as the ligands, together with various silver salts, to react with anion templates and we obtain ten silver chalcogenide clusters. What’s more, all compounds have been determined by single-crystal X-ray crystallography, elemental analysis, thermal analysis, flurescence spectroscopy and UV-Vis spectra. Moreover, we study their electrochemical properties and solution behavior of compounds.This thesis consists of three parts:Ⅰ:We briefly introduce the overview of metal cluster compound, mainly introduce the research progress of the sulfur silver clusters and acetylene cluster. And we also introduct the synthesis methods of silver clusters.Ⅱ:We use different thiol ligands and diphenylphosphine auxiliary ligand to react with silver salts and synthsize eight compounds, namely, [Ag9S(tBuC6H4S)6(dpph)3(CF3SO3)] (1),[Ag9(tBuC6H4S)6(dpph)3(CF3SO3)2]·CF3SO3 (2), [Ag9(tBuC6H4S)6(dpph)3(NO3)2]·NO3 (3), [Ag9(tBuC6H4S)7(dpph)3(Mo207)0.5]2·2CF3COO (4), (HNEt3)2[AgioS2(tBuC6H4S)6(dpppe)6]·Mo6O19·2DMF (5), [Ag6(tBuC6H4S)5(dppf)3]·BF4·DMF (6), (HNEt3)5[Ag6S(tBuC6H4S)4(dppf)3]·[Ag6S2(tBuC6H4S)3(dppf)3]·2Mo6O19 (7), [Ag7(tBuS)3(dppf)3(NO3)(H2O)]·3NO3 (8). The structures of compounds 1-4 describe a discrete molecule constructed from a girdling Ag9 twisted trigonal prism, which has a C3 symmetry.Herein, we developed a general route, that is, synergetic high steric-hindrance capping ligand and long diphosphine bridge, to isolate four similar C3-symmetric Ag9 clusters with a twisted trigonal-prism characteristic. This underlying principle was well-understood by compounds 5-8.Ⅲ:One-pot assembly of polymeric{(HNEt3)2[Ag10(SC6H4tBu)12]}n and CF3COOAg gives a novel ball-shaped {(HNEt3)[Ag37S4(SC6H4tBu)24(CF3COO)6(H2O)12]} cluster (9), which features a truncated tetrahedral geometry enwrapping an AgS4 tetrahedron in the center. To the best of ourknowledge, this Ag37 cluster is a very rare Keplerate formed bya Platonic solid templated Archimedean body.Moreover, we study their electrochemical properties and optical properties.Ⅳ:On the basis of the previous chapter, we added the anion template and synthesized a high nuclear silver clusters [Mo6O22@Ag58S2(SC6H4tBu)36(CF3COO)10(H2O)8] (10) templated by in situ generated Mo6O228- polyoxometalate, which is atomically precise polyoxometalate-Ag2S core-shellnanoparticles. This study exemplified the possibility to integratepolyoxometalate and Ag2S nanoparticles in to a core-shellheteronanostructure with precisely controlled the atomicalcompositions of both core and shell.