Yang Zhiwei, Wei Yanze, Wei Jingjing, Yang Zhijie
Key Laboratory of Colloid and Interface Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shandong University, Jinan, 250100, PR China.
Nat Commun. 2022 Oct 4;13(1):5844. doi: 10.1038/s41467-022-33638-6.
The development of mechanochemistry substantially expands the traditional synthetic realm at the molecular level. Here, we extend the concept of mechanochemistry from atomic/molecular solids to the nanoparticle solids, and show how the macroscopic grinding is being capable of generating chirality in self-assembled nanorod (NR) assemblies. Specifically, the weak van der Waals interaction is dominated in self-assembled NR assemblies when their surface is coated with aliphatic chains, which can be overwhelmed by a press-and-rotate mechanic force macroscopically. The chiral sign of the NR assemblies can be well-controlled by the rotating directions, where the clockwise and counter-clockwise rotation leads to the positive and negative Cotton effect in circular dichroism and circularly polarized luminescence spectra, respectively. Importantly, we show that the present approach can be applied to NRs of diverse inorganic materials, including CdSe, CdSe/CdS, and TiO. Equally important, the as-prepared chiral NR assemblies could be served as porous yet robust chiral substrates, which enable to host other molecular materials and induce the chirality transfer from substrate to the molecular system.
机械化学的发展在分子水平上极大地扩展了传统合成领域。在此,我们将机械化学的概念从原子/分子固体扩展到纳米颗粒固体,并展示了宏观研磨如何能够在自组装纳米棒(NR)聚集体中产生手性。具体而言,当自组装NR聚集体的表面涂有脂肪族链时,弱范德华相互作用在其中占主导地位,而宏观上的按压和旋转机械力可以克服这种相互作用。NR聚集体的手性符号可以通过旋转方向得到很好的控制,其中顺时针和逆时针旋转分别在圆二色性和圆偏振发光光谱中导致正和负的科顿效应。重要的是,我们表明目前的方法可以应用于多种无机材料的NRs,包括CdSe、CdSe/CdS和TiO。同样重要的是,所制备的手性NR聚集体可以用作多孔但坚固的手性底物,能够容纳其他分子材料并诱导手性从底物转移到分子体系。