Journal of the American Chemical Society · 2019 · 127 citations · 45 references
We report the synthesis and crystal structure determination of two novel chiral gold nanoclusters. By utilizing BINAP, we isolate atomically precise intrinsically chiral Au nanoclusters [Au<sub>9</sub>( R-/ S-BINAP)<sub>4</sub>](CF<sub>3</sub>COO)<sub>3</sub> and [Au<sub>10</sub>( R-/ S-BINAP)<sub>4</sub>( p-CF<sub>3</sub>C<sub>6</sub>H<sub>4</sub>C≡C)](CF<sub>3</sub>COO)<sub>3</sub> in high yield with one-pot synthesis. Au<sub>9</sub> has C<sub>2</sub> geometry, while Au<sub>10</sub> is C<sub>1</sub> symmetric. Interestingly, reversible interconversion between Au<sub>9</sub> and Au<sub>10</sub> can be realized by the addition or removal of a RC≡CAu component. The transformation from Au<sub>9</sub> to Au<sub>10</sub> leads to significant enhancement of CD signals. The maximum anisotropy factor in the visible region of [Au<sub>10</sub>(BINAP)<sub>4</sub>( p-CF<sub>3</sub>C<sub>6</sub>H<sub>4</sub>C≡C)]<sup>3+</sup> is the hitherto largest (up to 6.6 × 10<sup>-3</sup>) among gold nanoclusters, which is approximately twice of that of [Au<sub>9</sub>(BINAP)<sub>4</sub>]<sup>3+</sup>. This work demonstrates that the chiroptical activity of gold nanoclusters can be modulated by structural control through the introduction of second ligands.
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Amino-acid- and peptide-directed synthesis of chiral plasmonic gold nanoparticles
Hye‐Eun Lee, Hyo‐Yong Ahn, Jungho Mun et al. · Nature · 2018 · 1.2K citations