Controlling Ultra‐Large Optical Asymmetry in Amorphous Molecular Aggregations

Although ultra‐large optical asymmetry appears in crystalline materials, distractions from the mesoscopic ordering often causes inauthenticity in chiropticity. In amorphous materials, however, it remains challenging and elusive to achieve large chiropticity. Herein, we report the quantitative control of chiral amplification, on amorphous supramolecular structures of cholesteryl‐linked bis(dipyrrinato)zinc(II), to an exceptionally high level. A proper chiral packing of the building block at several molecular scale considerably contributes to the absorptive dissymmetry factor gabs, although the system is overall disordered. The intense and tunable aggregation strength renders a variable gabs value up to +0.10 and +0.31 in the solution and in film state. On this basis, a superior ON‐OFF switching of chiropticity is realized under external stimuli. This work establishes a general design principle to control over ultra‐large optical asymmetry on a wider scope of chiral materials. Cholesteryl‐linked bis(dipyrrinato)zinc(II) can be employed to construct beads‐like nanostructures with mirror‐image chiroptical signals. These nanostructures can further undergo a dynamic transformation to a homohelical leaf‐like morphology, together with an ON‐OFF switch of chiropticity at film state upon external stimuli. The ultra‐large optical asymmetry control is in amorphous molecular aggregations.