Manipulation of Liquid Crystalline Properties by Dynamic Covalent Chemistry─En Route to Adaptive Materials.

Abstract

Dynamic covalent bonds bear great potential for the development of adaptive and self-healing materials. Herein, we introduce a versatile concept not only for the design of low-molecular-weight liquid crystals but also for their in situ postsynthetic modification by using the dynamic covalent nature of imine bonds. The methodology allows systematic investigations of structure-property relationships as well as the manipulation of the materials' behavior (liquid crystallinity) and the introduction of additional properties (here, fluorescence) by a solvent-free method. For the first time, the transamination reaction is followed by variable-temperature 19F solid-state NMR in the mesophase, providing insights into the reaction dynamics in a liquid crystalline material. Finally, the application potential for the design of liquid crystalline materials with adaptive properties is demonstrated by a sequential combination of these reactions.