Induction, transmission, and manipulation of chirality in molecular systems are well known, widely applied concepts. However, our understanding of how chirality of nanoscale entities can be controlled, measured, and transmitted to the environment is considerably lacking behind. Future discoveries of dynamic assemblies engineered from chiral nanomaterials, with a specific focus on shape and size effects, require exact methods to assess transmission and amplification of nanoscale chirality through space. Here we present a remarkably powerful chirality amplification approach by desymmetrization of plasmonic nanoparticles to nanorods. When bound to gold nanorods, a one order of magnitude lower number of chiral molecules induces a tighter helical distortion in the surrounding liquid crystal–a remarkable amplification of chirality through space. The change in helical distortion is consistent with a quantification of the change in overall chirality of the chiral ligand decorated nanomaterials differing in shape and size as calculated from a suitable pseudoscalar chirality indicator.

Torsten (2019) 'Heliconical-layered nanocylinders (HLNCs) hierarchical self-assembly in a unique B4 phase liquid crystal morphology.', Materials horizons., 6 (5). 959968. Further information on publisher's website:https://doi.org/10.1039/C9MH00089EPublisher's copyright statement:Additional information: Use policyThe full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-prot purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details.

Polymorphism is a remarkable concept in chemistry, materials science, computer science, and biology. Whether it is the ability of a material to exist in two or more crystal structures, a single interface connecting to two different entities, or alternative phenotypes of an organism, polymorphism determines function and properties. In materials science, polymorphism can be found in an impressively wide range of materials, including crystalline materials, minerals, metals, alloys, and polymers. Here we report on polymorphism in a liquid crystal. A bent-core liquid crystal with a single chiral side chain forms two structurally and morphologically significantly different liquid crystal phases solely depending on the cooling rate from the isotropic liquid state. On slow cooling, the thermodynamically more stable oblique columnar phase forms, and on rapid cooling, a not heretofore reported helical microfilament phase. Since structure determines function and properties, the structural color for these phases also differs.

The creation and transmission of chirality in molecular systems is a well-known, widely applied notion. Our understanding of how the chirality of nanomaterials can be controlled, measured, transmitted through space, and applied is less well understood. Dynamic assemblies for chiral sensing or metamaterials engineered from chiral nanomaterials require exact methods to determine transmission and amplification of nanomaterial chirality through space. We report the synthesis of a series of gold nanorods (GNRs) with a constant aspect ratio of ∼4.3 capped with C 2 -symmetric, axially chiral binaphthyl thiols, preparation of dispersions in the nematic liquid crystal 5CB, measurements of the helical pitch, and the determination of the helical twisting power as well as the average distance between the chiral nanomaterial additives. By comparison to the neat organic chiral derivatives, we demonstrate how the amplification of chirality facilitated by GNRs decorated with chiral molecules can be used to clearly distinguish the chiral induction strength of a homologous series of binaphthyl derivatives, differing only in the length of the nontethered aliphatic chain, in the induced chiral nematic liquid crystal phase. Considering systematic errors in sample preparation and optical measurements, these chiral molecules would otherwise be deemed identical with respect to chiral induction. Notably, we find some of the highest ever-reported values of the helical twisting power. We further support our experimentally derived arguments of a more comprehensive understanding of chirality transfer by calculations of a suitable pseudoscalar chirality indicator.

In this work, we demonstrate control of the handedness of semicrystalline modulated helical nanofilaments (HNF mod s) formed by achiral bent-core liquid crystal molecules by axially chiral binaphthyl-based additives as guest molecules solely under spatial nanoconfinement in anodic aluminum oxide nanochannels. The molecules of the same chiral additives are expelled from the HNF mod s in the bulk, and as a result thereof do not affect the handedness or helical pitch of bulk HNF mod s, resulting in an HNF mod conglomerate with chiralitypreserving growth within each domain. However, under confinement these axially chiral guest molecules, likely embedded in the HNF mod host, do affect the helicity of the HNF mod s. The configuration of the axially chiral molecules decides the HNF mod helix handedness and their concentration, and the helix angle is related to the helical pitch of the HNF mod s. In addition to local imaging data obtained by scanning electron microscopy, global studies by thin-film circular dichroism spectropolarimetry support the imaging results.

The range of possible morphologies for bent‐core B4 phase liquid crystals has recently expanded from helical nanofilaments (HNFs) and modulated HNFs to dual modulated HNFs, helical microfilaments, and heliconical‐layered nanocylinders. These new morphologies are observed when one or both aliphatic side chains contain a chiral center. Here, the following questions are addressed: which of these two chiral centers controls the handedness (helicity) and which morphology of the nanofilaments is formed by bent‐core liquid crystals with tris‐biphenyl diester core flanked by two chiral 2‐octyloxy side chains? The combined results reveal that the longer arm of these nonsymmetric bent‐core liquid crystals controls the handedness of the resulting dual modulated HNFs. These derivatives with opposite configuration of the two chiral side chains now feature twice as large dimensions compared to the homochiral derivatives with identical configuration. These results are supported by density functional theory calculations and stochastic dynamic atomistic simulations, which reveal that the relative difference between the para‐ and meta‐sides of the described series of compounds drives the variation in morphology. Finally, X‐ray diffraction, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and atomic force microscopy (AFM) data also uncover the new morphology for B4 phases featuring p2/m symmetry within the filaments and less pronounced crystalline character.

The 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 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.

Chirality, as a concept, is well understood at most length scales. However, quantitative models predicting the efficacy of the transmission of chirality across length scales are lacking. We propose here a modus operandi for a chiral nanoshape solute in an achiral nematic liquid crystal host showing that that chirality transfer may be understood by unusually simple geometric considerations. This mechanism is based on the product of a pseudoscalar chirality indicator and of a geometric shape compatibility factor based on the two-dimensional isoperimetric quotients for each nanoshape solute. The model is tested on an experimental set of precisely engineered gold nanoshapes. These libraries of calculated and in-parallel acquired experimental data among related nanoshapes pave the way for predictive calculations of chirality transfer in nanoscale, macromolecular, and biological systems, from designing chiral discriminators and enantioselective catalysts to developing chiral metamaterials and understanding nature’s innate ability to transfer homochirality across length scales.