title: Binding motif of terminal alkynes on gold clusters.
abstract: Gold clusters protected by terminal alkynes (1-octyne (OC-H), phenylacetylene (PA-H) and 9-ethynyl-phenanthrene (EPT-H)) were prepared by the ligand exchange of small (diameter <2 nm) Au clusters stabilized by polyvinylpyrrolidone. The bonding motif of these alkynes on Au clusters was investigated using various spectroscopic methods. FTIR and Raman spectroscopy revealed that terminal hydrogen is lost during the ligand exchange and that the C≡C bond of the alkynyl group is weakened upon attachment to the Au clusters. Acidification of the water phase after the ligand exchange indicated that the ligation of alkynyl groups to the Au clusters proceeds via deprotonation of the alkynes. A series of precisely defined Au clusters, Au34(PA)16, Au54(PA)26, Au30(EPT)13, Au35(EPT)18, and Au(41-43)(EPT)(21-23), were synthesized and characterized in detail to obtain further insight into the interfacial structures. Careful mass analysis confirmed the ligation of the alkynes in the dehydrogenated form. An upright configuration of the alkynes on Au clusters was suggested from the Au to alkyne ratios and photoluminescence from the excimer of the EPT ligands. EXAFS analysis implied that the alkynyl carbon is bound to bridged or hollow sites on the cluster surface.
authors.affiliation: Department of Chemistry, School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
authors.forename: Prasenjit
authors.initials: P
authors.lastname: Maity
authors.forename: Shinjiro
authors.initials: S
authors.lastname: Takano
authors.forename: Seiji
authors.initials: S
authors.lastname: Yamazoe
authors.forename: Tomonari
authors.initials: T
authors.lastname: Wakabayashi
authors.forename: Tatsuya
authors.initials: T
authors.lastname: Tsukuda
mesh_terms: D000480:Alkynes / Q000737:chemistry*; D001665:Binding Sites; D006046:Gold / Q000737:chemistry*; D010316:Particle Size; D013499:Surface Properties
chemical_list: D000480:Alkynes; D006046:Gold