Au10(SG)10: A Chiral Gold Catenane Nanocluster with Zero Confined Electrons. Optical Properties and First-Principles Theoretical Analysis

被引：51

作者：

Bertorelle, Franck ^{[1
]}

Russier-Antoine, Isabelle ^{[1
]}

Calin, Nathalie ^{[2
]}

Comby-Zerbino, Clothilde ^{[1
]}

Bensalah-Ledoux, Arnina ^{[1
]}

Guy, Stephan ^{[1
]}

Dugourd, Philippe ^{[1
]}

Brevet, Pierre-Francois ^{[1
]}

Sanader, Zeljka ^{[3
,5
]}

Krstic, Marjan ^{[3
]}

Bonacic-Koutecky, Vlasta ^{[3
,4
]}

Antoine, Rodolphe ^{[1
]}

机构：

[1] Univ Claude Bernard Lyon 1, UMR 5306, Inst Lumiere Mat, CNRS, F-69622 Villeurbanne, France

[2] Univ Lyon 1, CNRS, Ecole Normale Super Lyon, Lab Chim,UMR 5182, 46 Allee Italie, F-69007 Lyon, France

[3] Univ Split, Ctr Excellence Sci & Technol Integrat Mediterrane, ICAST, Mestrovicevo Setaliste 45, HR-2100 Split, Croatia

[4] Humboldt Univ, Dept Chem, Brook Taylor Str 2, D-12489 Berlin, Germany

[5] Univ Split, Fac Sci, Rudera Bogkovica 33, HR-2100 Split, Croatia

来源：

JOURNAL OF PHYSICAL CHEMISTRY LETTERS | 2017年 / 8卷 / 09期

关键词：

METAL NANOCLUSTERS; THIN-FILMS; 2-PHOTON ABSORPTION; CLUSTERS; EVOLUTION; EMISSION; DESIGN;

D O I：

10.1021/acs.jpclett.7b00611

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

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.

引用

页码：1979 / 1985

页数：7

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