Kim Minseok, Tang Qing, Narendra Kumar Alam Venugopal, Kwak Kyuju, Choi Woojun, Jiang De-En, Lee Dongil
Department of Chemistry, Yonsei University , Seoul 03722, Korea.
Department of Chemistry, University of California , Riverside, California 92508, United States.
J Phys Chem Lett. 2018 Mar 1;9(5):982-989. doi: 10.1021/acs.jpclett.7b03261. Epub 2018 Feb 12.
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 cluster with Pt and Pd atoms leads to core-doped [PtAu(SCH)] and [PdAu(SCH)], respectively. Voltammetric investigations show that these clusters exhibit drastically different electronic structures; whereas the HOMO-LUMO gap of [PtAu(SCH)] is found to be 0.95 V, that of [PdAu(SCH)] 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 [PdAu(SCH)] reveals that the rod-like MAu core becomes more flattened upon Pd-doping. Reversible geometrical interconversion between [PtAu(SCH)] and [PtAu(SCH)] is clearly demonstrated by manipulating the oxidation state of the cluster.
杂原子掺杂是在原子水平上调节金簇光学和电子性质的有力手段。我们在此报告，用Pt和Pd原子掺杂金簇分别导致核掺杂的[PtAu(SCH)]和[PdAu(SCH)]。伏安研究表明，这些簇表现出截然不同的电子结构；[PtAu(SCH)]的HOMO-LUMO能隙为0.95 V，而[PdAu(SCH)]的能隙急剧降至0.26 V，表明12电子簇存在 Jahn-Teller 畸变。密度泛函研究证实，掺杂Pd的簇的HOMO-LUMO能隙确实减小。对12电子[PdAu(SCH)]优化几何结构的分析表明，掺杂Pd后，棒状MAu核变得更加扁平。通过操纵簇的氧化态，清楚地证明了[PtAu(SCH)]和[PtAu(SCH)]之间的可逆几何相互转化。
