Chiroptical Activity Enhancement via Structural Control: the Chiral Syn-thesis and Reversible Interconversion of Two Intrinsically Chiral Gold Nanoclusters,Journal of the American Chemical Society

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Chiroptical Activity Enhancement via Structural Control: the Chiral Syn-thesis and Reversible Interconversion of Two Intrinsically Chiral Gold Nanoclusters
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2019-01-18 , DOI: 10.1021/jacs.8b11096
Jia-Qi Wang ₁ , Zong-Jie Guan ₂ , Wen-Di Liu ₁ , Yang Yang ₃ , Quan-Ming Wang _{1,

2}

Affiliation

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.

中文翻译：

通过结构控制增强手性活性：两个本征手性金纳米团簇的手性合成和可逆互变

我们报告了两种新型手性金纳米团簇的合成和晶体结构测定。通过利用BINAP，我们分离出原子级精确的本征手性Au纳米团簇[Au9(R-/S-BINAP)4](CF3COO)3和[Au10(R-/S-BINAP)4(p-CF3C6H4C≡C)](CF3COO) )3 一锅法合成，收率高。Au9 具有 C2 几何形状，而 Au10 具有 C1 对称几何形状。有趣的是，Au9 和 Au10 之间的可逆互变可以通过添加或去除 RC≡CAu 组件来实现。从 Au9 到 Au10 的转变导致 CD 信号的显着增强。[Au10(BINAP)4(p-CF3C6H4C≡C)]3+在可见光区的最大各向异性因子是迄今为止金纳米团簇中最大的（高达6.6×10-3），约为[ Au9(BINAP)4]3+。

更新日期：2019-01-18

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