Self‐Assembly in Helical Columnar Mesophases and Luminescence of Chiral 1H‐Pyrazoles

Chiral polycatenar 1H‐pyrazoles self‐assemble to form columnar mesophases that are stable at room temperature. X‐ray diffraction and CD studies in the mesophase indicate a supramolecular helical organization consisting of stacked H‐bonded dimers. The liquid‐crystalline compounds reported are 3,5‐bis(dialkoxyphenyl)‐1H‐pyrazoles that incorporate two or four dihydrocitronellyl chiral tails. It can be observed that the grafting of these branched chiral substituents onto the 3,5‐diphenyl‐1H‐pyrazole core has a beneficial role in inducing mesomorphism, because isomeric linear‐chain compounds are not liquid crystalline; this is not the usual scheme of behavior. Furthermore, the molecular chirality is transferred to the columnar mesophase, because preferential helical arrangements are observed. Films of the compounds are luminescent at room temperature and constitute an example of the self‐organization of nondiscoid units into columnar liquid‐crystalline assemblies in which the functional molecular unit transfers its properties to a hierarchically built superstructure.     

Lyotropic Supramolecular Helical Columnar Phases Formed by C3‐Symmetric and Unsymmetric Rigid Molecules

Unlike thermotropic liquid‐crystalline C₃‐symmetric molecules with flexible chains, the herein‐designed fully rigid three‐armed molecules (C₃‐symmetric and unsymmetric) create a fancy architecture for the formation of lyotropic liquid crystals in water. First, hollow columns with triple‐stranded helices, analogous to helical rosette nanotubes, are spontaneously constructed by self‐organization of the rigid three‐armed molecules. Then, the helical nanotubes arrange into hexagonal liquid‐crystalline phases, which show macroscopic chirality as a result of supramolecular chiral symmetry breaking. Interestingly, the helical nanotubes constructed by the fully rigid molecules are robust and stable over a wide concentration range in water. They are hardly affected by ionic defects at the molecular periphery, that is, further decoration of functional groups on the molecular arms can presumably be realized without changing the helical conformation. In addition, the formed columnar phases can be aligned macroscopically by simple shear and show anisotropic ionic conductivity, which suggests promising applications for low‐dimensional ion‐conductive materials.     

Helical Carbon and Graphite Films Prepared from Helical Poly(3,4‐ethylenedioxythiophene) Films Synthesized by Electrochemical Polymerization in Chiral Nematic Liquid Crystals

Helical carbon and graphite films from helical poly(3,4‐ethylenedioxythiophene) (H‐PEDOT) films synthesized through electrochemical polymerization in a chiral nematic liquid‐crystal (N*‐LC) field are prepared. The microscope investigations showed that the H‐PEDOT film synthesized in the N*‐LC has large domains of one‐handed spiral morphology consisting of fibril bundles. The H‐PEDOT films exhibited distinct Cotton effects in circular dichroism spectra. The highly twisted N*‐LC with a helical pitch of smaller than 1 μm produced the H‐PEDOT film with a highly ordered morphology. The spiral morphologies with left‐ and right‐handed screws were observed for the carbon films prepared from the H‐PEDOT films at 800 °C and were well correlated with the textures and helical pitches of the N*‐LCs. The spiral morphologies of the precursors were also retained even in the graphite films prepared from the helical carbon films at 2600 °C.     

Helical Mechanoclinic Deformation of Main‐Chain Chiral Smectic Elastomers

The helical mechanoclinic deformation of a main‐chain chiral smectic elastomer, which is prepared by a crosslinking reaction under twist deformation, is investigated. The twist deformation induces a layer tilt angle that depends on the handedness of twist. The layer tilt angle in the right‐handedly twisted elastomer, of which the handedness is consistent with that of the helix in the SmC* phase of the non‐crosslinked backbone polymer, is estimated to be up to 16° at room temperature, although that in the left‐handedly twisted elastomer is less than several degrees. The experiments provide evidence of chiral coupling between tilt and twist for helical mechanoclinic deformation in the chiral smectic system.

     

Three‐Way‐Switchable (Right/Left/OFF) Selective Reflection of Circularly Polarized Light on Solid Thin Films of Helical Polymer Blends

Two poly(quinoxaline‐2,3‐diyl) copolymers bearing miscibility‐enhancing 8‐chlorooctyloxy and (S)‐2‐methylbutoxy or n‐butoxy side chains were synthesized. After annealing in CHCl₃ vapor, a polymer‐blend film of these copolymers exhibited selective reflection of right‐handed circularly polarized light (CPL) in the visible region. The handedness of the CPL reflected was completely inverted upon annealing of the film in THF vapor. Annealing in n‐hexane vapor resulted in the phase separation of the polymer blend, which turned the selective reflection off. This three‐way‐switchable reflection, that is, reflection of right‐handed or left‐handed CPL, together with an OFF state, could be observed visually through right‐ and left‐handed CPL filters.     

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.     

Functional Columnar Liquid Crystalline Phases From Ionic Complexes of Dendronized Polymers and Sulfate Alkyl Tails

We describe how cationic dendronized polymers of generations 1, and 2 and anionic monoalkyl tails can be combined by supramolecular ionic complexation into comb-like liquid crystalline polymers. The final structures in bulk of these supramolecular complexes were studied by differential scanning calorimetry (DSC), cross-polarized optical microscopy (CPOM), small angle x-rays scattering (SAXS) and transmission electron microscopy (TEM). The combination of these techniques allowed elucidating (i) that these complexes exhibit thermotropic behaviour, (ii) that various liquid crystalline structures in the 3–5 nm length scale can be obtained such as columnar rectangular, columnar tetragonal, columnar hexagonal and lamellar, depending both on alkyl tail length and polymer generation, (iii) that although the alkyl tails represent the majority phase in the columnar phases, they form the cylindric domains, and the dendronized polymers occupy the continuous domains. Therefore, upon selective cleavage of the alkyl tails in the columnar phases, the present self-assembly approach may constitute an efficient strategy towards the formation of porous organic matrices with ultra-dense pore size in the range of 2 to 4 nm.     

Advances in Metal‐Free Heterocycle‐Based Columnar Liquid Crystals

Liquid crystals are ordered soft materials formed by self‐organized molecules and can potentially be used as new functional materials for electron‐, ion‐ or molecular‐transport; optical; and bio‐active materials. In particular, the columnar liquid crystals are promising candidates used in various optical and electronic devices. For this purpose, design and synthesis of unconventional materials are essential. In this review, we have summarized several approaches for the synthesis of columnar liquid crystals composed of various heterocyclic systems. We also outline their liquid crystalline and other relevant properties, and their suitability for applications in diverse fields.     

Thermal‐ and Photo‐Induced Phase‐Transition Behaviors of a Tapered Dendritic Liquid Crystal with Photochromic Azobenzene Mesogens and a Bicyclic Chiral Center

A ribbon‐shaped chiral liquid crystalline (LC) dendrimer with photochromic azobenzene mesogens and an isosorbide chiral center (abbreviated as AZ₃DLC) was successfully synthesized and its major phase transitions were studied by using differential scanning calorimetry (DSC) and linear polarized optical microscopy (POM). Its ordered structures at different temperatures were further identified through structure‐sensitive diffraction techniques. Based on the experimental results, it was found that the AZ₃DLC molecule exhibited the low‐ordered chiral smectic (Sm*) LC phase with 6.31 nm periodicity at a high‐temperature phase region. AZ₃DLC showed the reversible photoisomerization in both organic solvents and nematic (N) LC media. As a chiral‐inducing agent, it exhibited a good solubility, a high helical‐twisting power, and a large change in the helical‐twisting power due to its photochemical isomerization in the commercially available N LC hosts. Therefore, we were able to reversibly “remote‐control” the colors in the whole visible region by finely tuning the helical pitch of the spontaneously formed helical superstructures.     

N‐Arylated 3,5‐Dihydro‐4H‐dinaphtho[2,1‐c:1′,2′‐e]azepines: Axially Chiral Donors with High Helical Twisting Powers for Nonplanar Push–Pull Chromophores

Axially chiral, N‐arylated 3,5‐dihydro‐4H‐dinaphtho[2,1‐c:1′,2′‐e]azepines have been prepared by short synthetic protocols from enantiopure 1,1′‐bi(2,2′‐naphthol) (BINOL) and anilines. Alkynes substituted with two N‐phenyldinaphthazepine donors readily undergo a formal [2+2] cycloaddition, followed by retro‐electrocyclization, with tetracyanoethene (TCNE) to yield donor‐substituted 1,1,4,4‐tetracyanobuta‐1,3‐dienes (TCBDs) featuring intense intramolecular charge‐transfer (CT) interactions. A dicyanovinyl derivative substituted with one N‐phenyldinaphthazepine donor was obtained by a “one‐pot” oxidation/Knoevenagel condensation from the corresponding propargylic alcohol. Comparative electrochemical, X‐ray crystallographic, and UV/Vis studies show that the electron‐donor qualities of N‐phenyldinaphthazepine are similar to those of N,N‐dimethylanilino residues. The circular dichroism (CD) spectrum of a push–pull chromophore incorporating the chiral donor moiety features Cotton effects of exceptional intensity. With their elongated shape and the rigidity of the chiral N‐aryldinaphthazepine donors, these chromophores are effective inducers of twist distortion in nematic liquid crystals (LCs). Thus, a series of the dinaphthazepine derivatives was used as dopants in the nematic LC E7 (Merck) and high helical twisting powers (β) of the order of hundreds of μm^?1 were measured. Theoretical calculations were employed to elucidate the relation between the structure of the dopants and their helical twisting power. For the derivatives with two dinaphthazepine moieties, a strong dependence of the β‐values on the structure and conformation of the linker between them was found.     

Predicting the Switchable Screw Sense in Fluorene‐Based Polymers

A chirality‐switching free‐energy landscape was reconstructed on a 43‐mer of poly(9,9‐dioctylfluoren‐2,7‐diyl) (PDOF). The simulations were conducted on amorphous silica surface as well as in the vacuum phase for a single chain or for a group of sixteen chains. The achiral‐to‐chiral transition occurs only on amorphous silica (activation free‐energy 35 kcal mol^?1), where the enantiomeric (homochiral) basins are detected. This was supported by the experiments where effective chirality induction to PDOF using circularly polarized light (CPL) was attained only for a film deposited on a quartz glass and not for a solution or a suspension. These results indicate that interactions of PDOF with amorphous silica play a crucial role in chirality switching. Importance of chain assembling was also indicated. Theoretical ECD spectra of the enantiomeric basins containing a 5₁ helix reproduce the experimental spectra.     

Self‐Assembly of Coronene Bisimides: Mechanistic Insight and Chiral Amplification

The study of the organization of small π‐conjugated molecules is imperative to understanding and controlling its properties for various applications. Coronene bisimides (CBIs) are potential candidates for novel liquid‐crystalline materials and active n‐type semiconductor molecules in organic electronics. To understand the self‐assembly of this seldom‐studied chromophore, we have designed two derivatives of CBIs bearing chiral and achiral 3,4,5‐trialkoxyphenyl groups at the imide position, named as CBI‐GCH and CBI‐GACH , respectively. CBI‐GCH self‐assembles mainly through π‐stacking and van der Waals interactions in nonpolar methylcyclohexane to result in long 1D fibrillar stacks. The mechanism of supramolecular polymerization was probed by using chiroptical studies, which showed an isodesmic pathway for CBI‐GCH . The thermodynamic parameters that govern the self‐assembly are detailed. CBI‐GACH also shows similar self‐assembly behavior as its chiral counterpart. X‐ray diffraction studies of both molecules reveals a 2D hexagonal columnar arrangement. The coassembly of CBI‐GCH and CBI‐GACH shows chiral amplification (sergeant and soldiers experiment) with saturation at 30–50 % of the chiral derivative, which was further used to study the dynamics of the assembly. Thus, this study presents a rare report of chiral amplification in an isodesmic system.     

Truxene‐Based Columnar Liquid Crystals: Self‐Assembled Structures and Electro‐Active Properties

Columnar liquid‐crystalline (LC) truxene derivatives containing branched flexible alkyl chains have been designed and synthesized. The dicyanomethylene and dithiafulvene substituents have been introduced into the π‐conjugated truxene framework to tune their electronic and redox properties as well as the molecular assembled structures. The π‐conjugated cores of dicyanomethylene‐ and dithiafulvene‐appended truxenes adopt bowl‐shaped conformations, giving rise to a large intrinsic dipole moment perpendicular to the aromatic framework. These molecules form stable columnar LC structures through intermolecular dipole–dipole interactions. The redox properties of LC truxene derivatives have been examined by cyclic voltammetry. The dicyanomethylene‐appended truxene shows the reversible four‐step electrochemical reductions, whereas the dithiafulvene‐appended truxene undergoes three‐step oxidations.     

Unexpected Thermally Stable,Cholesteric Liquid‐Crystalline Helical Polyisocyanides with Memory of Macromolecular Helicity

The achiral sodium salt of poly(4‐carboxyphenyl isocyanide) (poly‐ 1 –Na) folds into a one‐handed helix induced by optically active amines in water. The induced helicity remains when the optically active amines are completely removed, and further modification of the side groups to amide residues is possible without loss of memory of macromolecular helicity. Although the helical poly‐ 1 –Na loses its chiral memory at high temperature, helical polyisocyanides modified with achiral primary amines, which no longer have any chiral components, keep their memory perfectly even at 100 °C in N,N‐dimethylformamide in some cases and exhibit cholesteric liquid‐crystalline phases, thus providing a robust scaffold with heat resistance to which a variety of functional groups can be introduced.     

DNA‐Based Polymers as Chiral Templates for Second‐Order Nonlinear Optical Materials

The unique symmetry properties of chiral systems allow the emergence of coherent second harmonic generation in polymeric materials lacking polar order. Deoxyribonucleic acid (DNA) treated with the surfactant cetyltrimethylammonium (CTMA) was drop‐cast to spontaneously form films that are active for coherent second harmonic generation (SHG). SHG images acquired as a function of incident and exigent polarization are in good agreement with theoretical predictions assuming nonpolar D_∞ symmetry for the double‐stranded DNA chains. Doping the DNA films with crystal violet substantially increases the efficiency of SHG, but does not significantly alter the polarization‐dependence, suggesting that the SHG generated upon doping arises from the same chiral‐specific origin, presumably templated by the DNA. These results raise the possibility of new design strategies for organic nonlinear optical materials based on soft chiral polymers that do not require polar order.