Dynamically Tunable Assemblies of Superparamagnetic Nanoparticles Stabilized with Liquid Crystal-like Ligands in Organic Thin Films.

The process of arranging magnetic nanoparticles (MNPs) into long-range structures that can be dynamically and reversibly controlled is challenging, although interesting for emerging spintronic applications. Here, we report composites of MNPs in excess of LC-like ligands as promising materials for MNP-based technologies. The organic part ensures the assembly of MNP into long-range ordered phases as well as precise and temperature-reversible control over the arrangement. The dynamic changes are fully reversible, which we confirm using X-ray diffraction (XRD). This methodology allows for the precise control of the nanomaterial's structure in a thin film at different temperatures, translating to variable unit cell parameters. The composition of the materials (XPS, TGA), their structure (XRD), and magnetic properties (SQUID) were performed. Overall, this study confirms that LC-like materials provide the ability to dynamically control the magnetic nanoparticles in thin films, particularly the reversible control of their self-organization.

Tunable Circularly Polarized Luminescence via Chirality Induction and Energy Transfer from Organic Films to Semiconductor Nanocrystals.

Circularly polarized luminescent (CPL) films with high dissymmetry factors hold great potential for optoelectronic applications. Herein, we propose a strategy for achieving strongly dissymetric CPL in nanocomposite films based on chirality induction and energy transfer to semiconductor nanocrystals. First, focusing on a purely organic system, aggregation-induced emission (AIE) and CPL activity of organic liquid crystals (LCs) forming helical nanofilaments was detected, featuring green emission with high dissymmetry factors glum ∼ 10-2. The handedness of helical filaments, and thus the sign of CPL, was controlled via minute amounts of a small chiral organic dopant. Second, nanocomposite films were fabricated by incorporating InP/ZnS semiconductor quantum dots (QDs) into the LC matrix, which induced the chiral assembly of QDs and endowed them with chiroptical properties. Due to the spectral matching of the components, energy transfer (ET) from LC to QDs was possible enabling a convenient way of tuning CPL wavelengths by varying the LC/QD ratio. As obtained, composite films exhibited absolute glum values up to ∼10-2 and thermally on/off switchable luminescence. Overall, we demonstrate the induction of chiroptical properties by the assembly of nonchiral building QDs on the chiral organic template and energy transfer from organic films to QDs, representing a simple and versatile approach to tune the CPL activity of organic materials.

Thermomechanically controlled fluorescence anisotropy in thin films of InP/ZnS quantum dots.

Macroscopic scale sources of polarized light play a fundamental role in designing light-emitting devices. In this communication we report the formation of nano- and macro-scale ordered, layered assemblies of InP/ZnS quantum dots (QDs) exhibiting fluorescence anisotropy (FA), as well as thermo- and mechano-responsive properties. The long-range organization of small, quasi-isotropic nanoparticles was achieved by introducing liquid crystal molecules to the surface of QDs, without the need to use an organic matrix. Melting/crystallization of the ligand at 95 deg. C translated to a reversible reconfiguration of QDs thin film between 2D layered and body-centered cubic structures, characteristic for a temperature range below and above the melting point, respectively. The low-temperature, layered structure exhibited mechano-responsiveness which was key to introduce and control the sample alignment. Interestingly, transverse and parallel alignment modes of QDs layers were achieved, depending on the temperature of mechanical shearing. As prepared QD samples exhibited fluorescence anisotropy strongly correlated to the macroscopic orientation of the layers. Correlated small-angle X-ray diffraction (SAXRD) and fluorescence spectroscopy studies confirmed the mm-scale alignment of the thin films of QDs. Such films may be advantageous for developing efficient, densely packed, and uniform macro-scale FA sources.