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

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.