120th General Meeting of the KCS

Type Oral Presentation
Area Oral Presentation of Young Scholars in Electrochemistry
Room No. Room 201+202
Time THU 09:30-:
Code ELEC.O-3
Subject Effect of two dopants on the electronic structure of M2Au36(SC6H13)24 (M=Pt, Pd)
Authors Minseok Kim, Dongil Lee*, Kyuju Kwak
Department of Chemistry, Yonsei University, Korea
Abstract Over the past decade, owing to their unique electronic structures with high chemical and thermodynamic stability, thiolate ligand-protected gold nanoclusters have been extensively studied. Recently, bimetallic gold nanoclusters have been reported, which represents a viable strategy to study the sensitivity of physical-chemical properties of the nanoclusters towards replacement of a single or a few gold atoms by other metals. In particular, bimetallic MxAu38-x(SR)24 nanoclusters (M=Pd or Ag, SR=thiolate ligand) have been studied recently due to their excellent stability and different optical and electrochemical properties. In this presentation, we report the optical and electrochemical characteristics of stable bimetallic clusters ([Pd2Au36(SR)24]0 and [Pt2Au36(SR)24]2-) which showed different electronic configurations, by replacing the core Au atom with Pd and Pt. The gap between highest occupied molecular orbital-lowest unoccupied molecular orbitals of [Pd2Au36(SR)24]0 determined by voltammetry was drastically decreased to 0.26 eV, but that of [Pt2Au36(SR)24]2- was comparable with [Au38(SR)24]0 (0.94 eV), indicating the electronic structures could be altered upon doping of the foreign metal. This result could be illustrated by their different electron configurations, that is [Pd2Au36(SR)24]0 cluster having 12 superatomic electron exhibits remarkably different optical and electrochemical properties from those of the 14 electron cluster systems such as [Au38(SR)24]0 and [Pt2Au36(SR)24]2-.
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