Chiral Inversion of Thiolate-Protected Gold Nanoclusters via Core Reconstruction without Breaking an Au-S Bond
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Malola, S., & Häkkinen, H. (2019). Chiral Inversion of Thiolate-Protected Gold Nanoclusters via Core Reconstruction without Breaking an Au-S Bond. Journal of the American Chemical Society, 141 (14), 6006-6012. doi:10.1021/jacs.9b01204
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Journal of the American Chemical SocietyDate
2019Copyright
© 2019 American Chemical Society
Based on density functional theory
computations of the well-known chiral Au38(SR)24
nanocluster and its Pd- and Ag-doped derivatives,
we propose here a mechanism for chiral inversion
that does not require breaking of a metal-sulfur
bond at the metal-ligand interface, but features a
collective rotation of the gold core. The calculated
energy barriers for this mechanism for Au38 and Pddoped Au38 are in the range of 1 – 1.5 eV,
significantly lower than barriers involving breakage
of Au-S bonds (2.5 eV). For Ag-doped Au38, barriers
for both mechanisms are similar (1.3 – 1.5 eV).
Inversion barriers for a larger chiral Au144(SR)60 are
much higher (2.8 eV). Our computed barriers are in
a good agreement with racemization barriers
estimated from existing experiments for bare and
doped Au38. These results highlight the sensitivity of
chiral inversion to the size, structure and metal
composition of the metal core and sensitivity to the
detailed structure of the metal-thiolate interface.
Our work also predicts that enantiopure Au144(SR)60
clusters would be promising materials for
applications requiring high resistance to chiral
inversion.
...


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