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Published on: March 5, 2019
Chiroptical Activity Enhancement via Structural Control: The Chiral Synthesis and Reversible Interconversion of Two
Jia-Qi Wang1, Zong-Jie Guan2, Wen-Di Liu1
1Department of Chemistry , Tsinghua University , Beijing 10084 , PR China.
Abstract:
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 [Au9( R-/ S-BINAP)4](CF3COO)3 and [Au10( R-/ S-BINAP)4( p-CF3C6H4C≡C)](CF3COO)3 in high yield with one-pot synthesis. Au9 has C2 geometry, while Au10 is C1 symmetric. Interestingly, reversible interconversion between Au9 and Au10 can be realized by the addition or removal of a RC≡CAu component. The transformation from Au9 to Au10 leads to significant enhancement of CD signals. The maximum anisotropy factor in the visible region of [Au10(BINAP)4( p-CF3C6H4C≡C)]3+ is the hitherto largest (up to 6.6 × 10-3) among gold nanoclusters, which is approximately twice of that of [Au9(BINAP)4]3+. 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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