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.