Synthesis,Structure And Properties Of Coinage Metal Clusters Protected By O-Carboranylethynyl Ligands

The atomically precise coinage metal nanoclusters?NCs?have attracted much attention due to their aesthetically pleasing structure and interesting photophysical properties.These nanomaterials possess potential applications in various areas,including catalysis,sensing,medicine,energy conversion,and optoelectronics.Comparing to thiolate ligands,alkynyl ligands can adopt richer coordination modes,and generate a series of metal clusters with novel geometric configurations and unique optical properties.In addition,the introduction of foreign metal atoms into single-metal clusters to form alloy clusters is an effective way to optimize the performance of alkynyl coinage metal clusters.Based on the above analysis,a series of coinage metal clusters with intriguing properties were constructed by employing o-carboranylethylnyl ligands(9-HC?C-closo-1,2-C₂B₁₀H₁₁).The specific work content is as follows:1.AAg₁₄clusterwithhollowcagemetalstructure,{[Ag₁₄(C₂B₁₀H₁₁C₂)₁₂?CH₃CN?₂]Cl₂}·2CH₃CN?1?,has been synthesized by an one-pot synthetic method.Afterwards,isostructural two 2e superatomic clusters,{[Ag₈Cu₇(C₂B₁₀H₁₁C₂)₁₂]X}·6CH₃CN?2?and{[Ag₈Au₇(C₂B₁₀H₁₁C₂)₁₂?CH₃CN?₂]X}·6CH₃CN?3?,have been synthesized via alloying method and the self-reduction of o-carboranylethylnyl ligands.Compound 2 exhibits red photoluminescence.Finally,an anisotropic cluster,[Ag₃₃(C₂B₁₀H₁₁C₂)₂₀?apy?₂]?4?,has been successfully obtained by introducing 4-?anthracen-9-yl?pyridine ligand.2.A stable luminescent cluster{Au₇(C₂B₁₀H₁₁C₂)₆?tht?₂]Cl}·2CH₃CN?tht=tetrahydrothiophene??5?has been synthesized by reacting o-carboranylethylnyl ligands with Au?tht?Cl precusor.By adjusting the ratio of ligand and metal precursor during the synthesis,an1Dchaincompound{[Au₇(C₂B₁₀H₁₁C₂)₆?tht?₂][Au?tht?₂]?NO₃?Cl}?3CH₃CN?CH₂Cl₂?6?with interesting temperature-dependent luminescence has been obtained.To prepare Au nanoclusters with biger size and graceful complex structure,the reducing agent was employed during the identical synthetic procedure of 5,which led to the formation f a nanocluster[Au₂₈(C₂B₁₀H₁₁C₂)₁₂?tht?₈]³⁺?7?with face-centered cubic metal arrangement and 13valence electrons.The metal atomic arrangement of the cluster is highly similar to the Au₂₈ core in the reported Au₃₆.