Dopant-Dependent Electronic Structures Observed for M 2 Au 36 (SC 6 H 13 ) 24 Clusters (M = Pt, Pd).

Autor: Kim M; Department of Chemistry, Yonsei University , Seoul 03722, Korea., Tang Q; Department of Chemistry, University of California , Riverside, California 92508, United States., Narendra Kumar AV; Department of Chemistry, Yonsei University , Seoul 03722, Korea., Kwak K; Department of Chemistry, Yonsei University , Seoul 03722, Korea., Choi W; Department of Chemistry, Yonsei University , Seoul 03722, Korea., Jiang DE; Department of Chemistry, University of California , Riverside, California 92508, United States., Lee D; Department of Chemistry, Yonsei University , Seoul 03722, Korea.
Jazyk: angličtina
Zdroj: The journal of physical chemistry letters [J Phys Chem Lett] 2018 Mar 01; Vol. 9 (5), pp. 982-989. Date of Electronic Publication: 2018 Feb 12.
DOI: 10.1021/acs.jpclett.7b03261
Abstrakt: Heteroatom doping is a powerful means to tune the optical and electronic properties of gold clusters at the atomic level. We herein report that doping a Au 38 cluster with Pt and Pd atoms leads to core-doped [Pt 2 Au 36 (SC 6 H 13 ) 24 ] 2- and [Pd 2 Au 36 (SC 6 H 13 ) 24 ] 0 , respectively. Voltammetric investigations show that these clusters exhibit drastically different electronic structures; whereas the HOMO-LUMO gap of [Pt 2 Au 36 (SC 6 H 13 ) 24 ] 2- is found to be 0.95 V, that of [Pd 2 Au 36 (SC 6 H 13 ) 24 ] 0 is drastically decreased to 0.26 V, suggesting Jahn-Teller distortion of the 12-electron cluster. Density functional investigations confirm that the HOMO-LUMO gap of the Pd-doped cluster is indeed reduced. Analysis of the optimized geometry for the 12-electron [Pd 2 Au 36 (SC 6 H 13 ) 24 ] 0 reveals that the rod-like M 2 Au 21 core becomes more flattened upon Pd-doping. Reversible geometrical interconversion between [Pt 2 Au 36 (SC 6 H 13 ) 24 ] 0 and [Pt 2 Au 36 (SC 6 H 13 ) 24 ] 2- is clearly demonstrated by manipulating the oxidation state of the cluster.
Databáze: MEDLINE
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