Synthesis And Structure Of Copper(?) Alkynyl Clusters

The coinage metal?Cu^I,Ag^I,and Au^I?are frequently employed in the syntheses of novel cluster complexes due to their enhanced metallophilic interaction that overcomes repulsion between cationic metal centers.However,only several Cu?I?clusters have been reported,presumably due to the unstable nature of Cu?I?ion through air oxidation.Furthermore,the poor solubility of Cu?I?complexes makes the isolation of discrete clusters more challenging.We have synthesized and structurally characterized a series of copper?I?alkynyl complexes through different methods.The main contents of this thesis are as follows:?1?Four air-stable copper?I?alkynyl clusters protected by ^tBuC?C?ligand were synthesized by comproportionation reaction,using Cu?II?salt,Cu powder and tert-butyl acetylene as reactents.[Cu₁₄?^tBuC?C?₁₀?NO₃?₄?CH₃CN?]·2H₂O?1?[Cu₁₅?^tBuC?C?₁₄?NO₃?]?2?[Cu₁₄?^tBuC?C?₈?C₆H₅COO?₆]·C₆H₅CH₃?3?[Cu₁₅?^tBuC?C?₁₀?HCOO?₅]·CH₃OH?4?We have conducted a systematic investigation of various factors such as variation of the anion precursors and solvent employed that influence the formation of copper?I? alkynyl clusters.Complexes 1-4 exhibit obvious UV absorption,and they emit bright-orange fluorescence under UV light excitation.?2?Two copper?I?alkynyl clusters were constructed by three different ligands by reacting Cu₂O,^tBuC?CH,carboxylic acid and hexafluoroacetylacetone.[Cu₁₄?^tBuC?C?₈?hfac?₂?CF₃COO?₄]?5?[Cu₁₄?^tBuC?C?₈?hfac?₂?C₆H₅COO?₄]?6?The structure of compounds 5 and 6 indicates that the introduction of hfac^-ligands increase the solubility of alkynyl copper clusters.?3?Two 3D coordination compounds based on copper?I?alkynyl clusters were obtained by solvothermal reaction.{[Cu₁₄?^tBuC?C?₈?NO₃?₂?CN?₄]}_n?7?{[Cu₇?^tBuC?C?₄?CN?₃]}_n?8?Complexes 7 and 8 displays an intriguing 3D cyano-bridged Cu?I?alkynyl cluster-based framework,in which the existence of CN?is assumed to have originated from the Cu?I?-mediated C–C cleavage reaction of acetonitrile under mild solvothermal conditions.