Superhigh-ε materials that exhibit exceptionally high dielectric permittivity are recognized as potential candidates for a wide range of next-generation photonic and electronic devices. In general, achieving a high-ε state requires low material symmetry, as most known high-ε materials are symmetry-broken crystals. There are few reports on fluidic high-ε dielectrics. Here, we demonstrate how small molecules with high polarity, enabled by rational molecular design and machine learning analyses, enable the development of superhigh-ε fluid materials (dielectric permittivity, ε > 104) with strong second harmonic generation and macroscopic spontaneous polar ordering. The polar structures are confirmed to be identical for all the synthesized materials. Furthermore, adapting this strategy to high–molecular weight systems allows us to generalize this approach to polar polymeric materials, creating polar soft matters with spontaneous symmetry breaking.

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Recently, a type of ferroelectric nematic fluid has been discovered in liquid crystals in which the molecular polar nature at molecule level is amplified to macroscopic scales through a ferroelectric packing of rod-shaped molecules. Here, we report on the experimental proof of a polar chiral liquid matter state, dubbed helielectric nematic, stabilized by the local polar ordering coupled to the chiral helicity. This helielectric structure carries the polar vector rotating helically, analogous to the magnetic counterpart of helimagnet. The helielectric state can be retained down to room temperature and demonstrates gigantic dielectric and nonlinear optical responses. This matter state opens a new chapter for developing the diverse polar liquid crystal devices.

The emerging ferroelectric nematic (N F ) liquid crystal is a novel 3D-ordered liquid exhibiting macroscopic electric polarization. The combination of the ultrahigh dielectric constant, strong nonlinear optical signal, and high sensitivity to the electric field makes N F materials promising for the development of advanced liquid crystal electroopic devices. Previously, all studies focused on the rod-shaped small molecules with limited length (l) range and dipole moment (μ) values. Here, through the precision synthesis, we extend the aromatic rod-shaped mesogen to oligomer/polymer (repeat unit up to 12 with monodisperse molecular-weight dispersion) and increase the μ value over 30 Debye (D). The N F phase has a widespread existence far beyond our expectation and could be observed in all the oligomer/polymer length range. Notably, the N F phase experiences a nontrivial evolution pathway with the traditional apolar nematic phase completely suppressed, i.e., the N F phase nucleates directly from the isotropic liquid phase. The discovery of thte ferroelectric packing of oligomer/polymer rods not only offers the concept of extending the N F state to oligomers/polymers but also provides some previously overlooked insights in oxybenzoate-based liquid crystal polymer materials.

The construction of hierarchical nanostructures with precise morphological and dimensional control has been one of the ultimate goals of contemporary materials science and chemistry, and the emulation of tailor-made nanoscale superstructures realized in the nature, using artificial building blocks, poses outstanding challenges. Herein we report a one-pot strategy to precisely synthesize hierarchical nanostructures through an in-situ initiation-growth process from a liquid crystalline block copolymer. The assembly process, analogous to living chain polymerization, can be triggered by small-molecule, macromolecule or even nanoobject initiators to produce various hierarchical superstructures with highly uniform morphologies and finely tunable dimensions. Because of the high degree of controllability and predictability, this assembly strategy opens the avenue to the design and construction of hierarchical structures with broad utility and accessibility.