Free Space in Liquid Crystals-Molecular Design, Generation, and Usage

In the last 50 years, an important aim of molecular and materials design has been the generation of space for the uptake of guest molecules in macrocycles and cryptands, in dendrimers as monomolecular containers, and recently in porous networks like metal-organic and covalent organic frameworks. Such molecular, oligomeric, and polymeric materials can be applied for sensing, separation, catalysis, drug delivery, and gas storage, among others. The common goal is the recognition of molecules and their uptake into and release from an appropriate space. Typically, completely empty space is unfavorable in crystalline materials. Therefore, the elimination of molecules from the cavities is often accompanied by the collapse of the cavities, that is, by a change in the molecular conformation. In contrast to this solid matter, in which the cavities are rationally designed by covalent or coordinative bonds, liquid crystals (LCs) are fluid materials with high molecular mobility. Thus, the proposal of empty space in LCs is certainly a scientific provocation. However, various recent publications on columnar mesophases claim the existence of pores with low electron density or even completely empty space on the basis of X-ray and solid-state NMR studies. Although the latter may be debated, there are many examples in which LCs take up dopants such as polymerizable monomers in disclination lines, perdeuterated chains in the interstices between columns, or electron acceptors to fill mesogens with incommensurate building blocks, which eventually stabilize the LC phases. It seems that in LC science the generation and usage of free space has been studied only occasionally and were lucky discoveries rather than investigations based on rational design. This Account summarizes the research on the formal generation of void in LCs and highlights that rational design of molecules can lead to unconventional mesophases by efficient filling of the provided space, as was shown with shuttlecock mesogens and discotic mesogens related to the concept of complementary polytopic interactions. The topic was recently further developed by the investigation of shape-persistent star mesogens. Despite the formally empty space between their arms, they all form columnar liquid crystals. Such shape-persistent oligo(phenylenevinylene) molecules fill the void and efficiently nanosegregate by helical packing in columns and deformation of the molecular scaffold at the expense of the torsional energy. This inspired us to fill the intrinsic free space by guest molecules either via supramolecular or covalent bonds or just by physical mixing in order to avoid the increase in torsional energy and to stabilize the structure. This strategy led to complex filled liquid-crystalline matter with high structural control and may in the future be used for the design of organic electronic materials that are easily alignable for device applications.