Dynamic Stabilization of the Ligand-Metal Interface in Atomically Precise Gold Nanoclusters Au68 and Au144 Protected by meta-Mercaptobenzoic Acid
Tero, T.-R., Malola, S., Koncz, B., Pohjolainen, E., Lautala, S., Mustalahti, S., Permi, P., Groenhof, G., Pettersson, M., & Häkkinen, H. (2017). Dynamic Stabilization of the Ligand-Metal Interface in Atomically Precise Gold Nanoclusters Au68 and Au144 Protected by meta-Mercaptobenzoic Acid. ACS Nano, 11(12), 11872-11879. https://doi.org/10.1021/acsnano.7b07787
Published inACS Nano
DisciplineFysikaalinen kemiaOrgaaninen kemiaNanoscience CenterPhysical ChemistryOrganic ChemistryNanoscience Center
© 2017 American Chemical Society. This is a final draft version of an article whose final and definitive form has been published by ACS. Published in this repository with the kind permission of the publisher.
Ligand-stabilized, atomically precise gold nanoclusters with a metal core of a uniform size of just 1-3 nm constitute an interesting class of nanomaterials with versatile possibilities for applications due to their size-dependent properties and modifiable ligand layers. The key to extending the usability of the clusters in applications is to understand the chemical bonding in the ligand layer as a function of cluster size and ligand structure. Previously, it has been shown that monodispersed gold nanoclusters, stabilized by meta-mercaptobenzoic acid (m-MBA or 3-MBA) ligands and with sizes of 68-144 gold atoms, show ambient stability. Here we show that a combination of nuclear magnetic resonance spectroscopy, UV-vis absorption, infrared spectroscopy, molecular dynamics simulations, and density functional theory calculations reveals a distinct chemistry in the ligand layer, absent in other known thiol-stabilized gold nanoclusters. Our results imply a low-symmetry C1 ligand layer of 3-MBA around the gold core of Au68 and Au144 and suggest that 3-MBA protects the metal core not only by the covalent S-Au bond formation but also via weak π-Au and O=C-OH···Au interactions. The π-Au and -OH···Au interactions have a strength of the order of a hydrogen bond and thus are dynamic in water at ambient temperature. The -OH···Au interaction was identified by a distinct carbonyl stretch frequency that is distinct for 3-MBA-protected gold clusters, but is missing in the previously studied Au102(p-MBA)44 cluster. These thiol-gold interactions can be used to explain a remarkably low ligand density on the surface of the metal core of these clusters. Our results lay a foundation to understand functionalization of atomically precise ligand-stabilized gold nanoclusters via a route where weak ligand-metal interfacial interactions are sacrificed for covalent bonding. ...
PublisherAmerican Chemical Society
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Related funder(s)Academy of Finland
Funding program(s)Research post as Academy Research Fellow, AoF; Academy Project, AoF; Research costs of Academy Professor, AoF
Additional information about fundingThis work was supported by grants 258806, 266492, 290077, and 294217 from the Academy of Finland. H.H. acknowledges the Finnish Academy Professorship. The computations were done at the Nanoscience Center (NSC) in University of Jyvas̈ kylä and at the Finnish national supercomputer center CSC. We thank M. Azubel and R. D. Kornberg for sending samples of 3-MBA-protected Au68 and Au144 clusters for analysis as well as for numerous discussions while preparing the joint submission of papers and T. Tsukuda for discussions on the mass spectrometry data of Au144. ...
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