A Strategy for Polar Crystals with Dipolar Heterohelicenes.

Abstract

Polar crystals have attracted interest for the applications to polar materials with piezo- and pyroelectricity, and second harmonic generation. Despite their potential utility for flexible polar materials, a strategy for ordering polar helicenes has remained elusive. Here, we demonstrate the creation of polar crystals with unsymmetrically substituted aza[5]helicenes tuned by substituents. The unsymmetric aza[5]helicenes have been prepared through regioselective mono-protiodesilylations. We disclose that triisopropylsilyl-substituted derivatives show 1D chain columnar packings. In particular, enantiopure crystals showed spontaneous polarization. Optical and single-crystal X-ray diffraction experiments with other derivatives, as well as theoretical calculations, revealed that the presence of triisopropylsilyl or electron-withdrawing aryl substituents is essential for forming the 1D chain columnar structure. Hirshfeld surface analyses further showed that CH-π interactions between 1D chain columns regulate the polar assembly. Finally, we determined the polarizability of the nitro derivative by ab initio calculation to be 4.53 μC/cm2 . This value corroborates the first example of a spontaneously polar crystal of helicenes. We believe that this study will contribute to the development of polar materials from organic molecules.