Photoresponsive Chiral Dopants Research Articles

Chirality invertible superstructure mediated active planar optics

Active planar optical devices that can dynamically manipulate light are highly sought after in modern optics and nanophotonics. The geometric phase derived from the photonic spin-orbit interaction provides an integrated strategy. Corresponding elements usually suffer from static functions. Here, we introduce an inhomogeneously self-organized anisotropic medium featured by photo-invertible chiral superstructure to realize geometric phase elements with continuously tunable working spectrum and light-flipped phase profile. Via preprograming the alignment of a cholesteric liquid crystal mixed with a photo-responsive chiral dopant, we demonstrate light-activated deflector, lens, Airy beam and optical vortex generators. Their polychromatic working bands are reversibly tuned in an ultra-broadband over 1000 nm covering green to telecomm region. The chirality inversion triggers facile switching of functionalities, such as beam steering, focusing/defocusing and spin-to-orbital angular momentum conversion. This work offers a platform for advanced adaptive and multifunctional flat optics with merits of high compactness, low loss and broad bandwidth.

Photoresponsive Chiral Dopants: Light‐Driven Helicity Manipulation in Cholesteric Liquid Crystals for Optical and Mechanical Functions

AbstractThis Review focuses on recent advancements regarding the design of photoisomerizable chiral dopants which can switch the helical orientation in cholesteric liquid crystals upon light stimuli. Chiral dopants exhibiting conformational change in response to an external stimulus can provide dynamic control of the cholesteric pitch. Development of such responsive systems has been attempted since the 1970s. However, major advances on efficient chiral dopants exhibiting either high helical twisting power or large photoswitching have been achieved only in recent years. This Review covers photoresponsive low molecular weight cholesteric liquid crystal systems based on chiral dopants capable of photochemically “switching power to twist” surrounding liquid crystalline host molecules, “inverting” their handedness or even “inducing” helical organization from the racemic nematic phase.

Cholesteric films exhibiting expanded or split reflection bands prepared by atmospheric photopolymerisation of diacrylic nematic monomer doped with a photoresponsive chiral dopant

Cholesteric films exhibiting expanded or split reflection bands prepared by atmospheric photopolymerization of nematic diacrylate doped with a photoresponsive chiral dopant.

Light-induced rewiring and winding of Saturn ring defects in photosensitive chiral nematic colloids

We study the winding and unwinding of Saturn ring defects around silica microspheres with homeotropic surface anchoring in a cholesteric liquid crystal with a variable pitch. We use mixtures of a nematic liquid crystal 5CB and various photoresponsive chiral dopants to vary the helical pitch and sense of the helical winding by illuminating the mixtures with UV or visible light. Upon illumination, we observe motion of the Grandjean-Cano disclination lines in wedge-like cells. When the line touches the colloidal particle, we observe topological reconstruction of the Grandjean-Cano line and the Saturn ring. The result of this topological reconstruction is either an increase or decrease of the degree of winding of the Saturn ring around the colloidal particle. This phenomenon is similar to topological rewiring of -1/2 disclination lines, observed recently in chiral nematic colloids.

Macrocyclised pheynyl cinnamate dimer utilisable as photoresponsive chiral dopant for nematic liquid crystals

A macrocyclised phenyl cinnamate dimer with a chiral spacer was prepared, and its photochemistry was compared with that of a precursor linear dimer and corresponding monomeric compounds. Although ultraviolet irradiation of the monomer resulted merely in cis–trans isomerisation of a cinnamate, irradiation of the cyclic and linear dimers induced intra-molecular [2 + 2] photodimerisation of cinnamate groups. Photodimerisation in the cyclic dimer proceeded 20 times faster than in the linear dimer. In a nematic liquid crystal, the cyclic dimer exhibited a high helical twisting power of 27.5 μm−1, which decreased to 6.7 μm−1 with dimerisation. A macrocyclised dimer such as this can be used as a photoresponsive chiral dopant for nematic liquid crystals.

Influence of a Change in Helical Twisting Power of Photoresponsive Chiral Dopants on Rotational Manipulation of Micro‐Objects on the Surface of Chiral Nematic Liquid Crystalline Films

Herein we report a group of five planar chiral molecules as photon-mode chiral switches for the reversible control of the self-assembled superstructures of doped chiral nematic liquid crystals. The chiral switches are composed of an asymmetrically substituted aromatic moiety and a photoisomerizing azobenzene unit connected in a cyclic manner through methylene spacers of varying lengths. All the molecules show conformational restriction in the rotation of the asymmetrically substituted aromatic moiety in both the E and Z states of the azobenzene units resulting in planar chirality with separable enantiomers. Our newly synthesized compounds in pure enantiomeric form show high helical twisting power (HTP) in addition to an improved change in HTP between the E and Z states. The molecule with a diphenylnaphthalene unit shows the highest ever known initial helical twisting power among chiral dopants with planar chirality. In addition to the reversible tuning of reflection colors, we employed the enantiomers of these five compounds in combination with four nematic liquid crystalline hosts to study their properties as molecular machines; the change in HTP of the chiral dopant upon photoisomerization induces rotation of the texture of the liquid crystal surfaces. Importantly, this study has revealed a linear dependence of the ratio of the difference between HTPs before and after irradiation against the absolute value of the initial HTP, not the absolute value of the change in helical twisting power between two states, on the angle of rotation of micro-objects on chiral nematic liquid crystalline films. This study has also revealed that a change in irradiation intensity does not affect the maximum angle of rotation, but it does affect the speed of rotational reorganization of the cholesteric helix.

Photoinduced broadening of cholesteric liquid crystal reflectors

The selective reflection of cholesteric liquid crystals (CLCs) is well-known and has been utilized in a number of dynamic optical applications. This work presents a novel approach to passively (e.g., all-optically) cue reflection notch broadening in photoresponsive CLC formulations based on high helical twisting power (HTP) bis(azo) chiral dopants. The original reflection bandwidth of approximately 100 nm is increased to as much as 1700 nm, by exposing 36 μm thick cells to UV light. The maximum attainable bandwidth is shown to be a function of cell thickness, light intensity, and strongly related to the HTP of the photoresponsive chiral dopants. An all-optical technique of simultaneous UV and green light exposure is demonstrated to trap the reflection notch at a predetermined position and bandwidth.

Rewinding of Helical Systems by Use of the Cr(III) Complex as a Photoresponsive Chiral Dopant

Vibrational circular dichroism (VCD) spectroscopy has been applied for monitoring in situ the photoinduced rewind of supramolecular helices in a liquid crystal. The monitored system was a room-temperature liquid crystal, ZLI-1132, doped with a novel chiral Cr(III) complex. Under the illumination of UV light (365 nm), the photoracemization of the Cr(III) complex led to the rewind of helices in the chiral nematic phase. In response to this, the VCD spectrum of the system exhibited the transient change, confirming the elongation of helical pitch length. The possibility of using the VCD spectrum as a memory of photoresponsive events is discussed.

Photochemical Switching of Ferroelectric Liquid Crystals Using a Photoswitchable Chiral Dopant

Abstract Fast optical switching (response time 90 μs) was achieved of ferroelectric liquid crystals doped with a photoresponsive chiral dopant having an azobenzene moiety.