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In recent years, π-conjugated liquid crystalline molecules with optoelectronic functionalities have garnered considerable attention, and integrating these molecules into side-chain liquid crystalline polymers (SCLCPs) holds potential for developing devices that are operational near room temperature. However, it is difficult to design SCLCPs with excellent processability because liquid crystalline mesogens are rigid rods, have low solubility in organic solvents, and have a high isotropization temperature. Recently, we developed near-room-temperature π-conjugated nematic liquid crystals based on "bridged stilbene". In this work, we synthesized a polyacrylate SCLCP incorporating a bridged stilbene that exhibited a nematic phase near room temperature and could maintain liquid crystallinity for more than three months. We conducted a thorough phase structure analysis and evaluated the optical properties. The birefringence values of the resulting polymers were higher than those of the corresponding monomers because of the enhanced order parameters due to the polymer effect. In addition, the synthesized polymers inherited mesogen-derived AIE properties, with high quantum yields (Φfl = 0.14–0.35) in the solid state. It is noteworthy that the maximum fluorescence wavelength exhibited a redshift of greater than 27 nm as a consequence of film formation. Thus, several unique characteristics of the SCLCPs are unattainable with small molecular systems. [ABSTRACT FROM AUTHOR]

Supramolecular liquid crystals (SLCs) are attractive materials for fabricating devices with new optoelectronic functions. Conventional SLCs are made from hydrogen‐bonded mesogens. However, these mesogens suffer from high melting points, and the types of formable aggregates are limited owing to the directionality of the hydrogen bonding. Therefore, to fabricate non‐hydrogen‐bonded SLCs, we hypothesized that the introduction of tertiary amide groups into calamitic molecules would be advantageous because they have an L‐shaped structure with N‐ or C‐alkyl side chains not aligned along the long axis and the flexibility to undergo cis–trans isomerization. In this study, we developed a novel non‐hydrogen‐bonded SLC by assembling an L‐shaped dimer composed of calamitic molecules (phenyltolanes) with tertiary amides at their ends. These molecules exhibited a smectic B phase. The phase transition temperature of the SLCs from crystal to liquid crystal phase was low despite the long π‐conjugated core. Wide‐angle X‐ray diffraction and variable‐temperature Fourier‐transform infrared measurements revealed dimer formation by weak intermolecular interactions, that is, the molecular recognition of L‐shaped molecules, and mobility of the alkyl groups attached to amide driven by cis–trans isomerization in the liquid crystal phase. Thus, cis–trans isomerization of tertiary amides contributed enormously to the formation and lower clearing points of this SLC. The developed method can be used not only to develop non‐hydrogen‐bonded SLCs but also to develop novel soft matter with controlled properties by incorporating the SLCs, as the aggregates can be controlled to impart desired functionalities. [ABSTRACT FROM AUTHOR]

Multiple emission colors in solid-state organic fluorophores with the same main skeleton are essential for improving the performance of light-emitting devices/materials. Specifically, emission in the red/near-infrared region is of great importance in the biological field. Previously, we developed di-bridged-distyrylbenzene DBDB[7] with high-brightness solid-state blue and aggregation-induced emissions (AIE) by introducing the bridging structures of a seven-membered ring into the vinylene groups of distyrylbenzene (DSB). Herein, we synthesize MNDBDMeODB[7] (1), which features substituted methoxy and malononitrile groups as donor and acceptor groups, respectively, in DBDB[7]. In solvents more polar than THF, MNDSDMeOB (3), which has the same main skeleton as 1 but without bridges, shows no emission in the solid state, whereas 1 exhibits highly bright red-orange emission in the solid state owing to the suppression of intermolecular electronic interactions by the bridges and the AIE property. We also synthesize MNDSD(EHO)B (2) in which the methoxy groups of 3 are replaced by ethylhexyloxy groups, thus disrupting the crystallinity of the molecule. 2 exhibits positive fluorescence solvatochromism and has a high fluorescence quantum yield in the solid state as a red-emitting DSB derivative. The solid-state emission properties of 1 and 2 will improve the applicability of DSBs and functionalities of light-emitting devices/materials., (© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

To design ultrabright fluorescent solid dyes, a crystal engineering strategy that enables monomeric emission by blocking intermolecular electronic interactions is required. We introduced propylene moieties to distyrylbenzene (DSB) as bridges between the phenyl rings either side of its C=C bonds. The bridged DSB derivatives formed compact crystals that emit colors similar to those of the same molecules in dilute solution, with high quantum yields. The introduction of flexible seven-membered rings to the DSB core produced moderate distortion and steric hindrance in the DSB π-plane. However, owing to this strategy, it was possible to control the molecular arrangement with almost no decrease in the crystal density, and intermolecular electronic interactions were suppressed. The bridged DSB crystal structure differs from other DSB derivative structures; thus, bridging affords access to novel crystalline systems. This design strategy has important implications in many fields and is more effective than the conventional photofunctional molecular crystal design strategies., (© 2022 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)