Dopant-Dependent Electronic Structures Observed forM2Au36(SC6H13)24 Clusters (M = Pt, Pd)


Dopant-Dependent Electronic Structures Observed for M2Au36(SC6H13)24 Clusters (M = Pt, Pd)


Minseok Kim,† Qing Tang,‡ Alam Venugopal Narendra Kumar,† Kyuju Kwak,† Woojun Choi,† De-en Jiang,*,‡ and Dongil Lee*,†



Abstract


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 Au38 cluster with Pt and Pd atoms leads to core-doped [Pt2Au36(SC6H13)24] 2− and [Pd2Au36(SC6H13)24] 0 , respectively. Voltammetric investigations show that these clusters exhibit drastically different electronic structures; whereas the HOMO−LUMO gap of [Pt2Au36(SC6H13)24] 2− is found to be 0.95 V, that of [Pd2Au36(SC6H13)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 [Pd2Au36(SC6H13)24] 0 reveals that the rod-like M2Au21 core becomes more flattened upon Pd-doping. Reversible geometrical interconversion between [Pt2Au36(SC6H13)24]0 and [Pt2Au36(SC6H13)24]2− is clearly demonstrated by manipulating the oxidation state of the cluster.



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