title: Synthesis and Properties Evolution of a Family of Tiara-like Phenylethanethiolated Palladium Nanoclusters.
abstract: Tiara-like thiolated group 10 transition metal (Ni, Pd, Pt) nanoclusters have attracted extensive interest due to their fundamental scientific significance and potential application in a number of fields. However, the properties (e.g. the absorption) evolution with the ring size's increase was not investigated so far to our best knowledge, due to the challenge of obtaining a series of nanocluster analogues. Herein, we successfully synthesized, isolated and identified a family of [Pd(SC2H4Ph)2]n nanoclusters (totally 17 novel clusters, n = 4-20). Their structures were determined to be tiara-like by single crystal X-ray crystallography together with theoretical calculation; their formation mechanism was proposed to be a substitution-polycondensation-ring-closure process based on experimental observations. All of these clusters are rather robust (anti-reductive and anti-oxidative) owing to their tiara-like structures with large HOMO-LUMO gaps. Finally, the optical and electrochemical evolution with the increase of ring size was investigated, and it is found that both optical and electrochemical gaps have a "turning point" at a size corresponding to n = 8 for [Pd(SR)2]n nanoclusters.
authors.affiliation: Key Laboratory of Materials Physics, Anhui Key Laboratory of Nanomaterials and Nanotechnology, Institute of Solid State Physics, Chinese Academy of Sciences, Hefei 230031, China.|Department of Materials Science and Engineering, University of Science and Technology of China, Hefei, 230026, China.
authors.forename: Jishi
authors.initials: J
authors.lastname: Chen
authors.affiliation: Hefei National Laboratory for Physics Sciences at the Microscale, University of Science and Technology of China, Hefei, 230026, China.
authors.forename: Liren
authors.initials: L
authors.lastname: Liu
authors.affiliation: Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Department of Chemistry, Fudan University, Shanghai, 200433, China.
authors.forename: Linhong
authors.initials: L
authors.lastname: Weng
authors.affiliation: Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Department of Chemistry, Fudan University, Shanghai, 200433, China.
authors.forename: Yuejian
authors.initials: Y
authors.lastname: Lin
authors.affiliation: Key Laboratory of Materials Physics, Anhui Key Laboratory of Nanomaterials and Nanotechnology, Institute of Solid State Physics, Chinese Academy of Sciences, Hefei 230031, China.
authors.forename: Lingwen
authors.initials: L
authors.lastname: Liao
authors.affiliation: Hefei National Laboratory for Physics Sciences at the Microscale, University of Science and Technology of China, Hefei, 230026, China.
authors.forename: Chengming
authors.initials: C
authors.lastname: Wang
authors.affiliation: Hefei National Laboratory for Physics Sciences at the Microscale, University of Science and Technology of China, Hefei, 230026, China.
authors.forename: Jinlong
authors.initials: J
authors.lastname: Yang
authors.affiliation: Key Laboratory of Materials Physics, Anhui Key Laboratory of Nanomaterials and Nanotechnology, Institute of Solid State Physics, Chinese Academy of Sciences, Hefei 230031, China.
authors.forename: Zhikun
authors.initials: Z
authors.lastname: Wu