Conventional liquid-crystalline (LC) semiconductors have been molecules consisting of a π-conjugated moiety and alkyl
chains. For example, phenylterthiophene derivatives bearing alkyl chains exhibit ordered smectic phase at room
temperature and are applied to field-effect transistors. In this paper, we report a molecular designs of LC electronic
materials based on nanosegregation. Terthiophene derivatives bearing an imdazolium moiety exhibit supremolecular
smectic phases, in which hole- and ion-conductive layers are formed separately. In the LC phase, electrochrmism is
observed under the application of a DC bias without any electrolyte solutions. In simple side-chain LC polysiloxanes
bearing terthiophene pendant groups, suprastructures based on nanosegregation are observed. The presence of flexible
sublayers consisting of the polysiloxane backbones can relax the applied strain and decrease defect density, resulting in
high hole mobility on the order of 10-2 cm2/Vs. For perylene tetracarboxylic bisimide (PTCBI) derivatives bearing
oligosiloxane chains, nanosegregation between the rigid aromatic cores and flexible oligosiloxane chains promotes the
formation of columnar and layer structures, in which efficient electron transport is observed. The electron mobility in the
columnar phase of the PTCBI derivative bearing four trisiloxane chains exceeds 10-3 cm2/Vs at room temperature.
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