The significance of nanoparticle shape in chirality transfer to a surrounding nematic liquid crystal reporter medium

This perspective reports on recent progress toward the development of an approach to a priori predict - both chirality "strength" and efficacy of chirality transfer from a chiral nanoshape solute to an achiral nematic environment

Highly Tunable Circularly Polarized Emission of an Aggregation-Induced Emission Dye Using Helical Nano- and Microfilaments as Supramolecular Chiral Templates

International audienceAggregation-induced emission (AIE)-based circularly polarized luminescence (CPL) has been recognized as a promising pathway for developing chiroptical materials with high luminescence dissymmetry factors (|g(lum)|). Here, we propose a method for the construction of a thermally tunable CPL-active system based on a supramolecular self-assembly approach that utilizes helical nano- or microfilament templates in conjunction with an AIE dye. The CPL properties of the ensuing ensembles are predominantly determined by the intrinsic geometric differences among the various filament templates such as their overall dimensions (width, height, and helical pitch) and the area fraction of the exposed aromatic segments or sublayers. The proposed mechanism is based on the collective data acquired by absorption, steady state and time-resolved fluorescence, absolute quantum yield, and CPL measurements. The highest |g(lum)| value for the most promising dual-modulated helical nanofilament templates in the present series was further enhanced, reaching up to |g(lum)| = 0.25 by confinement in the appropriate diameter of anodized aluminum oxide (AAO) nanochannels. It is envisioned that this methodology will afford new insights into the design of temperature-rate indicators or anti-counterfeiting tags using a combination of structural color by the nano- and microfilament templates and the AIE property of the guest dye

Molecular conformation of bent-core molecules affected by chiral side chains dictates polymorphism and chirality in organic nano- and microfilaments

https://kent-islandora.s3.us-east-2.amazonaws.com/node/14391/83901-thumbnail.jpgThe coupling between molecular conformation and chirality is a cornerstone in the construction of supramolecular helical structures of small molecules across various length scales. Inspired by biological systems, conformational preselection and control in artificial helical molecules, polymers, and aggregates has guided various applications in optics, photonics, and chiral sorting among others, which are frequently based on an inherent chirality amplification through processes such as templating and self-assembly. The so-called B4 nano- or microfilament phase formed by some bent-shaped molecules [1-5] is an exemplary case for such chirality amplification across length scales, best illustrated by the formation of distinct nano- or microscopic chiral morphologies controlled by molecular conformation. Introduction of one or more chiral centers in the aliphatic side chains led to the discovery of homochiral helical nanofilament, helical microfilament, and heliconical-layered nanocylinder morphologies. Herein, we demonstrate how a priori calculations of the molecular conformation affected by chiral side chains are used to design bent-shaped molecules that self-assemble into chiral nano- and microfilament as well as nanocylinder conglomerates despite the homochiral nature of the molecules. Furthermore, relocation of the chiral center leads to formation of helical as well as flat nanoribbons. Self-consistent data sets from polarized optical as well as scanning and transmission electron microscopy, thin film and solution circular dichroism spectropolarimetry, and synchrotron-based X-ray diffraction experiments support the progressive and predictable change in morphology controlled by structural changes in the chiral side chains. The formation of these morphologies is discussed in light of the diminishing effects of molecular chirality as the chain length increases or as the chiral center is moved away from the core-chain juncture. The type of phase (B1-columnar or B4) and morphology of the nano- or microfilaments generated can further be controlled by sample treatment conditions such as by the cooling rate from the isotropic melt or by the presence of an organic solvent in the ensuing colloidal dispersions. We show that these nanoscale morphologies can then organize into a wealth of two- and three-dimensional shapes and structures ranging from flower blossoms to fiber mats formed by intersecting flat nanoribbons. References: [1] L. Li, M. Salamonczyk, A. Jakli, T. Hegmann, Small 2016, 12, 3944. [2] L. Li, M. Salamonczyk, S. Shadpour, C. Zhu, A. Jakli, T. Hegmann, Nat Commun 2018, 9, 714. [3] S. Shadpour, A. Nemati, N. J. Boyd, L. Li, M. E. Prévôt, S. L. Wakerlin, J. P. Vanegas, M. Salamończyk, E. Hegmann, C. Zhu, M. R. Wilson, A. I. Jákli, T. Hegmann, Materials Horizons 2019, 6, 959. [4] S. Shadpour, A. Nemati, J. Liu, T. Hegmann, ACS Appl Mater Interfaces 2020, 12, 13456. [5] S. Shadpour, A. Nemati, M. Salamonczyk, M. E. Prevot, J. Liu, N. J. Boyd, M. R. Wilson, C. Zhu, E. Hegmann, A. I. Jakli, T. Hegmann, Small 2020, 16, e1905591.</p

Significant Enhancement of the Chiral Correlation Length in Nematic Liquid Crystals by Gold Nanoparticle Surfaces Featuring Axially Chiral Binaphthyl Ligands

Chirality is a fundamental scientific concept best described by the absence of mirror symmetry and the inability to superimpose an object onto its mirror image by translation and rotation. Chirality is expressed at almost all molecular levels, from single molecules to supramolecular systems, and present virtually everywhere in nature. Here, to explore how chirality propagates from a chiral nanoscale surface, we study gold nanoparticles functionalized with axially chiral binaphthyl molecules. In particular, we synthesized three enantiomeric pairs of chiral ligand-capped gold nanoparticles differing in size, curvature, and ligand density to tune the chirality transfer from nanoscale solid surfaces to a bulk anisotropic liquid crystal medium. Ultimately, we are examining how far the chirality from a nanoparticle surface reaches into a bulk material. Circular dichroism spectra of the gold nanoparticles decorated with binaphthyl thiols confirmed that the binaphthyl moieties form a cisoid conformation in isotropic organic solvents. In the chiral nematic liquid crystal phase, induced by dispersing the gold nanoparticles into an achiral anisotropic nematic liquid crystal solvent, the binaphthyl moieties on the nanoparticle surface form a transoid conformation as determined by imaging the helical twist direction of the induced cholesteric phase. This suggests that the ligand density on the nanoscale metal surfaces provides a dynamic space to alter and adjust the helicity of binaphthyl derivatives in response to the ordering of the surrounding medium. The helical pitch values of the induced chiral nematic phase were determined, and the helical twisting power (HTP) of the chiral gold nanoparticles calculated to elucidate the chirality transfer efficiency of the binaphthyl ligand capped gold nanoparticles. Remarkably, the HTP increases with increasing diameter of the particles, that is, the efficiency of the chirality transfer of the binaphthyl units bound to the nanoparticle surface is diminished as the size of the particle is reduced. However, in comparison to the free ligands, per chiral molecule all tested gold nanoparticles induce helical distortions in a 10- to 50-fold larger number of liquid crystal host molecules surrounding each particle, indicating a significantly enhanced chiral correlation length. We propose that both the helicity and the chirality transfer efficiency of axially chiral binaphthyl derivatives can be controlled at metal nanoparticle surfaces by adjusting the particle size and curvature as well as the number and density of the chiral ligands to ultimately measure and tune the chiral correlation length