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Racemization of a Chiral Nanoparticle Evidences the Flexibility of the Gold–Thiolate Interface

Published in Journal of the American Chemical Society. 2012, vol. 134, no. 31, p. 13114-13120
Abstract Thiolate-protected gold nanoparticles and clusters combine size-dependent physical properties with the ability to introduce (bio)chemical functionality within their ligand shell. The engineering of the latter with molecular precision is an important prerequisite for future applications. A key question in this respect concerns the flexibility of the gold – sulfur interface. Here we report the first study on racemization of an intrinsically chiral gold nanocluster, Au38(SCH2CH2Ph)24, which goes along with a drastic rearrangement of its surface involving place exchange of several thiolates. This racemization takes place at modest temperatures (40 – 80 °C) without significant decomposition. The experimentally determined activation energy for the inversion reaction is ca 28 kcal/mol, which is surprisingly low considering the large rearrangement. The activation parameters furthermore indicate that the process occurs without complete Au-S bond breaking.
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Other version: http://pubs.acs.org/doi/abs/10.1021/ja3053865
Research group Groupe Bürgi
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KNOPPE, Stefan, DOLAMIC, Igor, BUERGI, Thomas. Racemization of a Chiral Nanoparticle Evidences the Flexibility of the Gold–Thiolate Interface. In: Journal of the American Chemical Society, 2012, vol. 134, n° 31, p. 13114-13120. https://archive-ouverte.unige.ch/unige:22048

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Deposited on : 2012-08-14

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