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. 2019 Mar 19;9(3):457.
doi: 10.3390/nano9030457.

Catenane Structures of Homoleptic Thioglycolic Acid-Protected Gold Nanoclusters Evidenced by Ion Mobility-Mass Spectrometry and DFT Calculations

Clothilde Comby-Zerbino  1 , Martina Perić  2 , Franck Bertorelle  3 , Fabien Chirot  4 , Philippe Dugourd  5 , Vlasta Bonačić-Koutecký  6   7 , Rodolphe Antoine  8
Affiliations

Catenane Structures of Homoleptic Thioglycolic Acid-Protected Gold Nanoclusters Evidenced by Ion Mobility-Mass Spectrometry and DFT Calculations

Clothilde Comby-Zerbino et al. Nanomaterials (Basel). .

Abstract

Thiolate-protected metal nanoclusters have highly size- and structure-dependent physicochemical properties and are a promising class of nanomaterials. As a consequence, for the rationalization of their synthesis and for the design of new clusters with tailored properties, a precise characterization of their composition and structure at the atomic level is required. We report a combined ion mobility-mass spectrometry approach with density functional theory (DFT) calculations for determination of the structural and optical properties of ultra-small gold nanoclusters protected by thioglycolic acid (TGA) as ligand molecules, Au10(TGA)10. Collision cross-section (CCS) measurements are reported for two charge states. DFT optimized geometrical structures are used to compute CCSs. The comparison of the experimentally- and theoretically-determined CCSs allows concluding that such nanoclusters have catenane structures.

Keywords: DFT calculations; catenane; gold nanoclusters; ion mobility; thiolate.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Figure 1
Figure 1
Experimental absorption spectra of Au10(SR)10 nanoclusters (NCs) (with SR = thioglycolic acid (TGA)and SG (see [7]). (Inset) Electrospray ionization ESI mass spectrum of the as-synthesized Au10(TGA)10 NCs.
Figure 2
Figure 2
TD-DFT absorption spectrum and structure for three lowest energy isomers of Au10(TGA)10 shown in (a–c) respectively. Leading excitations responsible for the characteristic features of absorption are illustrated on the right side. HOMO-LUMO for isomers I, II, and III are 4.54, 4.62, and 5.55 eV, respectively.
See this image and copyright information in PMC

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