Chirality evolution from molecule levels to the nanoscale in an achiral system is a fundamental issue that remains undiscovered. Here, we report the assembly of polyoxometalate (POM) clusters into chiral subnanostructures in achiral systems by programmable single-molecule interactions. Driven by the competing binding of Ca²⁺ and surface ligands, POM assemblies would twist into helical nanobelts, nanorings, and nanotubes with tunable helicity. Chiral molecules can be used to differentiate the formation energies of chiral isomers and immobilize the homochiral isomer, where strong circular dichroism (CD) signals are obtained in both solutions and films. Chiral helical nanobelts can be used as circularly polarized light (CPL) photodetectors due to their distinct chiroptic responsivity for right and left CPL. By the fine-tuning of interactions at single-molecule levels, the morphology and CD spectra of helical assemblies can be precisely controlled, providing an atomic precision model for investigation of the structure–chirality relationship and chirality manipulation at the nanoscale.

中文翻译：

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通过分子相互作用的明智控制来调节非手性亚纳米系统的手性演化

非手性系统中从分子水平到纳米尺度的手性演化是一个尚未发现的基本问题。在这里，我们报告了通过可编程单分子相互作用将多金属氧酸盐（POM）簇组装成非手性系统中的手性亚纳米结构。在Ca ²⁺和表面配体竞争性结合的驱动下，POM 组装体将扭曲成具有可调螺旋性的螺旋纳米带、纳米环和纳米管。手性分子可用于区分手性异构体的形成能并固定纯手性异构体，在溶液和薄膜中都能获得强圆二色性 (CD) 信号。手性螺旋纳米带由于其对左右 CPL 具有不同的手性响应性，可用作圆偏振光 (CPL) 光电探测器。通过单分子水平上相互作用的微调，可以精确控制螺旋组装体的形貌和圆二色光谱，为研究纳米尺度的结构-手性关系和手性操纵提供原子精度模型。