Liquid crystals with color-tunable light emission are important for a variety of applications; however, achieving multicolor light-emitting liquid crystals whose emission colors can be fine-tuned remains challenging because the limited derivatization of mesogenic fluorophores disfavors the diversity of the emission. Here, we present a positional isomerism-mediated copolymerization strategy to obtain liquid-crystalline polymers with continuous luminescence color-tuning ability. The introduced α−/β-cyanostilbene positional isomers possess very similar molecular structures, thus reducing the risk of assembly heterogeneity and facilitating the formation of a homogeneous and consistent liquid crystal mesophase. Meanwhile, a significant electronic effect was caused for fluorophores with positional isomerization, allowing the efficient tuning of emission colors via copolymerization. Especially with a gradual change in the composition of the copolymers, the emission color shift behaved in a continuous manner from blue to green. These cyanostilbenebased liquid-crystalline polymers also showed reversible photochromic fluorescence switching ability. This approach highlights the value of positional isomers to prepare color-tunable solid-state light-emitting materials, allowing control and fine-tuning of the emission property while maintaining the ordered assembly ability.
Most organic thermochromic fluorescent materials exhibit thermo-induced hypsochromic emission due to the formation of excimers in ordered molecular solids; however, it is still a challenge to endow them with bathochromic emission despite its significance in making up the field of thermochromism. Here, a thermo-induced bathochromic emission in columnar discotic liquid crystals is reported realized by intramolecular planarization of the mesogenic fluorophores. A three-armed discotic molecule of dialkylamino-tricyanotristyrylbenzene was synthesized, which preferred to twist out of the core plane to accommodate ordered molecular stacking in hexagonal columnar mesophases, giving rise to bright green monomer emission. However, intramolecular planarization of the mesogenic fluorophores occurred in isotropic liquid increasing the conjugation length, and as a result led to thermo-induced bathochromic emission from green to yellow light. This work reports a new concept in the thermochromic field and provides a novel strategy to achieve fluorescence tuning from intramolecular actions.
Segregated assembly in a π-conjugated donor−acceptor molecular system is imperative to create heterojunctions for optoelectronic applications. Here, we report lamellarly segregated columnar donor−acceptor arrays based on liquid crystalline alternating copolymers to afford high ambipolar and balanced charge mobilities. Especially, the rational molecular design renders the formation of a highly ordered hexagonal columnar superlattice based on the alternate lamellar structures. The ideal lamellar columnar heterojunction with regular distribution of donor−acceptor columns and remarkable intracolumnar order enables highly efficient and balanced hole and electron mobilities of 0.68 and 3.60 cm 2 V −1 s −1 , respectively. This work demonstrates the unique selforganization process of alternating copolymers containing two electronically active constituents and provides new insights into the design of ambipolar semiconducting soft materials for electronic and photovoltaic applications.
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