We synthesized cyclic chiral compounds [(R)/(S)-D2s] by linking a photoresponsive bisbenzothienylethene (BTE) moiety with an axially chiral binaphthyl moiety. Chiral nematic liquid crystals (N*-LCs) were prepared by adding chiral compounds as dopants to host N-LCs. These N*-LCs exhibited reversible chirality inversion upon photoisomerization between the open and closed forms of the BTE moiety. Here, the mechanism underlying chirality inversion in photoresponsive N*-LCs was investigated by comparing the helical twisting powers (HTPs) of (R)-D2s with those of analogous compounds. It was found that the helical inversion of N*-LCs containing (R)-D2s is governed by a delicate balance between two types of opposite helicity, i.e., the right-handed helicity of the inherently chiral binaphthyl moiety and the left-handed helicity of the BTE moiety bearing intramolecularly induced chirality. Namely, (R)-D2s induced chirality of the BTE moiety, which is attributed to intramolecular chirality transfer from the axially chiral binaphthyl moiety to the BTE moiety. Thus, (R)-D2s are chiral compounds with double chirality consisting of an intrinsically chiral moiety and an intramolecularly induced chiral moiety. Photocontrol of the helical senses and reversible photoinversion of the N*-LCs are achieved by utilizing UV and visible light irradiation and the steric effects of the substituents at the binaphthyl rings in (R)-D2s. In addition, photocontrol of the induced circularly polarized luminescence (CPL) was achieved using the photoinvertible N*-LC. The achiral aromatic conjugated copolymers that exhibited red, green, and blue fluorescence were dissolved and mixed in the present N*-LC, and they exhibited left- and right-handed white CPL with large dissymmetry factors (|glum|) ranging from 0.2 to 1.0. The CPLs were reversibly photoswitched due to photoisomerization between the open and PSS forms of the chiral compounds through UV and visible light irradiation.
Keywords: chiral compound; chirality control; intramolecular chirality transfer; liquid crystal; photoinversion.