A photoactivated chiral molecular clamp rotated by selective anion binding

Abstract

Developing chiral molecular platforms that respond to external fields provides opportunities for designing smart chiroptical materials. Herein, we introduce a molecular clamp whose chiral properties can be turned on by photoactivation. Selective anion binding achieves rational tuning of the conformations and chiroptical properties of the clamp, including circular dichroism and circularly polarized luminescence. Cyanostilbene segments were conjugated to chiral amines with a rotatable axis. Negligible chiroptical signals were significantly enhanced through a light illumination-induced isomerization. Binding with halide ions (F⁻, Cl⁻ and Br⁻) enables chiroptical inversion and subsequent amplification of the resulting opposite handedness state by photo treatment. In contrast, the larger I⁻ and NO₃⁻ ions failed to achieve chiroptical inversion. Also the handedness inversion was hampered in conformationally locked amines. Density-functional theory-based computational studies and experimental results reveal a structural transformation that proceeds from a butterfly-like open geometry to a closed V-shaped state initiated by four hydrogen bonds and the rotatable axis. This work illustrates design protocols for use in smart chiroptical molecular platforms mediated by photo treatment and anion binding.