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Bent colloidal rods exhibit fascinating polar ordering and chirality formation despite the achiral nature of the rods., Bent-core liquid crystal (LC) molecules are known to form mesophases with fascinating polar order and supramolecular chirality despite the achiral nature of the mesogens. The assembly of colloidal particles with geometrical similarity to bent-core molecular mesogens not only provides new insights into the physical behaviors of atoms or molecules but also leads to new materials with broad applications. Despite tremendous progress in colloidal synthesis and assembly, there has been a lack of colloidal model systems of bent-core molecular mesogens for LC property discovery and application development. This article describes a systematic study on the phase behaviors of colloidal analogs of bent-core LC mesogens in both experiments and simulations. We demonstrated that bent rods with controlled bending angle (α) and aspect ratio (L/D, with L and D as the length and diameter of each rod arm, respectively) can spontaneously assemble into several typical banana phases including smectic A, smectic C, synclinic tilted antiferroelectric-like smectic, and twist smectic phases, resembling bent-core LC molecules. The formation and transition of these phases were found to be strongly dependent on the geometric parameters of rods. Phase diagrams were developed to illustrate the existence and stability range of all the LC phases in α and L/D space. This work opens the door to the development of novel complex types of molecular or colloidal self-organization and new functional materials with electro-optical or nonlinear optical properties.

The design and assembly of novel colloidal particles are of both academic and technological interest. We developed a wet-chemical route to synthesize monodisperse bent rigid silica rods by controlled perturbation of emulsion-templated growth. The bending angle of the rods can be tuned in a range of 0–50° by varying the strength of perturbation in the reaction temperature or pH in the course of rod growth. The length of each arm of the bent rods can be individually controlled by adjusting the reaction time. For the first time we demonstrated that the bent silica rods resemble banana-shaped liquid-crystal molecules and assemble into ordered structures with a typical smectic B2 phase. The bent silica rods could serve as a visualizable mesoscopic model for exploiting the phase behaviors of bent molecules which represent a typical class of liquid-crystal molecules.