Conspectus
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.