Au-10(SG)(10): A Chiral Gold Catenane Nanocluster with Zero Confined Electrons. Optical Properties and First-Principles Theoretical Analysis

作者：Bertorelle Franck; Russier Antoine Isabelle; Calin Nathalie; Comby Zerbino Clothilde; Bensalah Ledoux Arnina; Guy Stephan; Dugourd Philippe; Brevet Pierre Francois; Sanader Zeljka; Krstic Marjan; Bonacic Koutecky Vlasta; Antoine Rodolphe^*

来源：Journal of Physical Chemistry Letters, 2017, 8(9): 1979-1985.

DOI：10.1021/acs.jpclett.7b00611

We report facile synthesis of the Au-10(SG)(10) nanoclusters, where SG stands for glutathione, found to be promising as a new class of radiosensitizers for cancer radiotherapy. The homoleptic catenane structure with two Au(5)SG(5) interconnected rings, among different isomer structures, gives the best agreement between theoretical and experimental optical spectra and XRD patterns. This catenane structure exhibits a centrosymmetry-broken structure, resulting in enhanced second harmonic response and new characteristic circular dichroism signals in the spectral region of 250-400 nm. This is the first determination of the nonlinear optical properties of a ligated cluster with an equal Au-to-ligand ratio, thus without a metallic core and therefore zero confined electrons. Insight into the nonlinear and chiroptical efficiencies arising from interplay between structural and electronic properties is provided by the TD-DFT approach.

• 出版日期2017-5-4