Rapid bulk assembly of nanoparticles into microstructures is challenging, but highly desirable for applications in controlled release, catalysis, and sensing. We report a method to form hollow microstructures via a two-stage nematic nucleation process, generating size-tunable closed-cell foams, spherical shells, and tubular networks composed of closely packed nanoparticles. Mesogen-modified nanoparticles are dispersed in liquid crystal above the nematic-isotropic transition temperature (TNI). On cooling through TNI, nanoparticles first segregate into shrinking isotropic domains where they locally depress the transition temperature. On further cooling, nematic domains nucleate inside the nanoparticle-rich isotropic domains, driving formation of hollow nanoparticle assemblies. Structural differentiation is controlled by nanoparticle density and cooling rate. Cahn-Hilliard simulations of phase separation in liquid crystal demonstrate qualitatively that partitioning of nanoparticles into isolated domains is strongly affected by cooling rate, supporting experimental observations that cooling rate controls aggregate size. Microscopy suggests the number and size of internal voids is controlled by second-stage nucleation.

When nanoparticle self-assembly takes place in an anisotropic liquid crystal environment, fascinating new effects can arise. The presence of elastic anisotropy and topological defects can direct spatial organization. An important goal in nanoscience is to direct the assembly of nanoparticles over large length scales to produce macroscopic composite materials; however, limitations on spatial ordering exist due to the inherent disorder of fluid-based methods. In this paper we demonstrate the formation of quantum dot clusters and spherical capsules suspended within spherical liquid crystal droplets as a method to position nanoparticle clusters at defined locations. Our experiments demonstrate that particle sorting at the isotropic–nematic phase front can dominate over topological defect-based assembly. Notably, we find that assembly at the nematic phase front can force nanoparticle clustering at energetically unfavorable locations in the droplets to form stable hollow capsules and fractal clusters at the droplet centers.

Liquid crystal (LC) phase transition dynamics can be used as a powerful tool to control the assembly of dispersed nanoparticles. Tailored mesogenic ligands can both enhance and tune particle dispersion in the liquid crystal phase to create liquid crystal nano-composites-a novel type of material. Soft nanocomposites have recently risen to prominence for their potential usage in a variety of industrial applications such as photovoltaics, photonic materials, and the liquid crystal laser. Our group has developed a novel phase-transition-templating process for the generation of micron-scale, vesicle-like nanoparticle shells stabilized by mesogenic ligand-ligand interactions. The mesogenic ligand's flexible arm structure enhances ligand alignment with the local LC director, providing control over the dispersion and stabilization of nanoparticles in liquid crystal phases. In this paper we explore the capsule formation process in detail, generating QDbased capsules over a surprisingly wide range of radii. We demonstrate that the initial nanoparticle concentration and cooling rate are important parameters influencing capsule size. By increasing particle concentration of nanoparticles and reducing the cooling rate we developed large shells up to 96±19 μm in diameter whereas decreasing concentration and increasing the cooling rate produces shells as small as 4±1 μm.

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The design, synthesis, properties, and performance of a new class of promesogenic calamitic side-tethering organic ligands used to direct quantum dot nanoparticle self-assembly are described. This work was motivated by inadequate modularity, step count, and yield associated with syntheses of existing ligands. Attaching the new ligands to quantum dots and dispersing them in a liquid crystal host affords hollow micrometer-sized capsules via phase transition templating. The capsules resist thermal decomposition up to 350 °Csignificantly higher than any previously reported microcapsules assembled from side-tethering calamitic ligand-functionalized nanoparticles. These novel ligands can be used for encapsulation applications where stability under high temperature is required. Evaluation of the capsules by smallangle X-ray scattering shows that interparticle spacing varies from 10 to 13 nm depending on the ligand used and is correlated to aminoalkyl chain length.