title: Chiral phase transfer and enantioenrichment of thiolate-protected Au₁₀₂ clusters.
abstract: The Au102(p-MBA)44 cluster (p-MBA: para-mercaptobenzoic acid) is observed as a chiral compound comprised of achiral components in its single-crystal structure. So far the enantiomers observed in the crystal structure are not isolated, nor is the circular dichroism spectrum known. A chiral phase transfer method is presented which allows partial resolution of the enantiomers by the use of a chiral ammonium bromide, (-)-1R,2S-N-dodecyl-N-methylephedrinium bromide ((-)-DMEBr). At sufficiently low concentration of (-)-DMEBr, the phase transfer from water to chloroform is incomplete. Both the aqueous and organic phases show optical activity of near mirror image relationship. Differences in the spectra are ascribed to the formation of diastereomeric salts. At high concentrations of (-)-DMEBr, full phase transfer is observed. The organic phase, however, still displays optical activity. We assume that one of the diastereomers has very strong optical activity, which overrules the cancelation of the spectra with opposite sign. Comparison with computations further corroborates the experimental data and allows a provisional assignment of handedness of each fraction.
authors.affiliation: Department of Chemistry, Molecular Imaging and Photonics, KU Leuven , Celestijnenlaan 200D, 3001 Heverlee, Belgium.
authors.forename: Stefan
authors.initials: S
authors.lastname: Knoppe
authors.forename: O Andrea
authors.initials: OA
authors.lastname: Wong
authors.forename: Sami
authors.initials: S
authors.lastname: Malola
authors.forename: Hannu
authors.initials: H
authors.lastname: Häkkinen
authors.forename: Thomas
authors.initials: T
authors.lastname: Bürgi
authors.forename: Thierry
authors.initials: T
authors.lastname: Verbiest
authors.forename: Christopher J
authors.initials: CJ
authors.lastname: Ackerson