Visible-Light-Driven Halogen Bond Donor Based Molecular Switches: From Reversible Unwinding to Handedness Inversion in Self-Organized Soft Helical Superstructures.

Visible-light-driven molecular switches endowing reversible modulation of the functionalities of self-organized soft materials are currently highly sought after for fundamental scientific studies and technological applications. Reported herein are the design and synthesis of two novel halogen bond donor based chiral molecular switches that exhibit reversible photoisomerization upon exposure to visible light of different wavelengths. These chiral molecular switches induce photoresponsive helical superstructures, that is, cholesteric liquid crystals, when doped into the commercially available room-temperature achiral liquid crystal host 5CB, which also acts as a halogen-bond acceptor. The induced helical superstructure containing the molecular switch with terminal iodo atoms exhibits visible-light-driven reversible unwinding, that is, a cholesteric-nematic phase transition. Interestingly, the molecular switch with terminal bromo atoms confers reversible handedness inversion to the helical superstructure upon irradiation with visible light of different wavelengths. This visible-light-driven, reversible handedness inversion, enabled by a halogen bond donor molecular switch, is unprecedented.

The Halogen Bond: An Emerging Supramolecular Tool in the Design of Functional Mesomorphic Materials.

Owing to their dynamic attributes, non-covalent supramolecular interactions have enabled a new paradigm in the design and fabrication of multifunctional material systems with programmable properties, performances, and reconfigurable traits. Recently, the "halogen bond" has become an enticing supramolecular synthetic tool that displays a plethora of promising and advantageous characteristics. Consequently, this versatile and dynamic non-covalent interaction has been extensively harnessed in various fields such as crystal engineering, self-assembly, materials science, polymer chemistry, biochemistry, medicinal chemistry and nanotechnology. In recent years, halogen bonding has emerged as a tunable supramolecular synthetic tool in the design of functional liquid-crystalline materials with adjustable phases and properties. In this Concept article, the use of halogen bond in the field of stimuli-responsive smart soft materials, that is, liquid crystals is discussed. The design, synthesis and characterization of molecular and macromolecular liquid crystalline materials are described and the modulation of their properties has been emphasized. The power of halogen bonding in offering a large variety of functional liquid crystalline materials from readily accessible mesomorphic and non-mesomorphic complementary building blocks is highlighted. The article concludes with a perspective on the challenges and opportunities in this emerging endeavor towards the realization of enabling and elegant dynamic functional materials.

Photochemically and Thermally Driven Full-Color Reflection in a Self-Organized Helical Superstructure Enabled by a Halogen-Bonded Chiral Molecular Switch.

Supramolecular approaches toward the fabrication of functional materials and systems have been an enabling endeavor. Recently, halogen bonding has been harnessed as a promising supramolecular tool. Herein we report the synthesis and characterization of a novel halogen-bonded light-driven axially chiral molecular switch. The photoactive halogen-bonded chiral switch is able to induce a self-organized, tunable helical superstructure, that is, cholesteric liquid crystal (CLC), when doped into an achiral liquid crystal (LC) host. The halogen-bonded switch as a chiral dopant has a high helical twisting power (HTP) and shows a large change of its HTP upon photoisomerization. This light-driven dynamic modulation enables reversible selective reflection color tuning across the entire visible spectrum. The chiral switch also displays a temperature-dependent HTP change that enables thermally driven red, green, and blue (RGB) reflection colors in the self-organized helical superstructure.

Electro- and Photo-Driven Orthogonal Switching of a Helical Superstructure Enabled by an Axially Chiral Molecular Switch.

Self-organized functional soft materials, enabled by specific chemical architectures, are currently attracting tremendous attention because of their stimuli-responsive attributes and applications in advanced technological devices. A novel axially chiral molecular switch containing two azo linkages and six terminal alkyl chains on two elongated rod-shaped wings, that exhibits superior solubility, high helical twisting power, and reversible photoisomerization in an achiral liquid crystal host, is synthesized and utilized in the development of a photoresponsive, self-organized helical superstructure, that is, cholesteric liquid crystal (CLC). The planar CLC adopts a standing helix (SH) configuration because of surface alignment layers on the substrates. This SH can be transitioned to a lying helix configuration, enabling tunable diffraction gratings under the application of electric field. Adjustment of the initial pitch of the planar CLC by photoirradiation yields the diffraction gratings with stripes either parallel or perpendicular to the rubbing direction upon the application of an appropriate electric field. Tunable beam steering along orthogonal directions has been demonstrated. Such tunable stimuli-responsive soft materials fabricated with artificial chiral switches show great potential in optics, photonics, and beyond.

Dynamic Orthogonal Switching of a Thermoresponsive Self-Organized Helical Superstructure.

Controllable manipulation of self-organized dynamic superstructures of functional molecular materials by external stimuli is an enabling enterprise. Herein, we have developed a thermally driven, self-organized helical superstructure, i.e., thermoresponsive cholesteric liquid crystal (CLC), by integrating a judiciously chosen thermoresponsive chiral molecular switch into an achiral liquid crystalline medium. The CLC in lying state, in both planar and twisted nematic cells, exhibits reversible in-plane orthogonal switching of its helical axis in response to the combined effect of temperature and electric field. Consequently, the direction of the cholesteric grating has been observed to undergo 90° switching in a single cell, enabling non-mechanical beam steering along two orthogonal directions. The ability to reversibly switch the cholesteric gartings along perpendicular directions by appropriately adjusting temperature and electric field strength could facilitate their applications in 2D beam steering, spectrum scanning, optoelectronics and beyond.

Red, green and blue reflections enabled in an optically tunable self-organized 3D cubic nanostructured thin film.

A new light-driven chiral molecular switch doped in a stable blue phase (BP) liquid crystal allows wide optical tunability of three-dimensional cubic nanostructures with a selective reflection wavelength that is reversibly tuned through the visible region. Moreover, unprecedented reversible light-directed red, green, and blue reflections of the self-organized three-dimensional cubic nanostructure in a single film are demonstrated for the first time. Additionally, unusual isothermal photo-stimulated less ordered BP II to more ordered BP I phase transition was observed in the system.