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.
Highlights
Thiolate-protected metal nanoclusters (NCs) are a promising class of nanomaterials due to fascinating molecular-like properties along with well-defined molecular structures [1,2,3]
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
The catenane-like staple motifs predicted for Au15(SR)13 and Au24(SR)20 suggest that, at a Au/SR ratio approaching 1/1, the interlocked staple motifs may become a widespread conformation in thiolate-protected metal nanoclusters [8,9,10]
Summary
Thiolate-protected metal nanoclusters (NCs) are a promising class of nanomaterials due to fascinating molecular-like properties along with well-defined molecular structures [1,2,3]. Ion mobility spectrometry (IMS) has been used for the characterization of gas-phase ligand-protected metal nanoclusters [12,13,14,15,16,17,18,19]. The IMS technique was not sufficient to discriminate between different possible structures (in particular catenane structures) for the core This discrimination could be easier if smaller and more rigid ligands are used for protection, where charge-induced ligand unfolding effects will be minimized. In this case, the structural characterization of clusters may be possible by comparing the arrival time distribution profiles recorded by ion mobility mass spectrometry with theoretical calculations using molecular modelling (density functional theory, DFT) and subsequent collision cross-section calculations using projection approximation. The comparison of the experimentally- and theoretically-determined CCSs allows concluding about the catenane structures of such nanoclusters
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