Molecular Design and Alignment for Ambipolar SCLC Mobility in Self-Assembled Columnar Discogens.

The future of next-generation electronics relies on low-cost organic semiconductors that are tailored to simultaneously provide all requisite optoelectronic properties, focusing greatly on ambipolar charge-transport and solution processability. In this regard, room-temperature discotic liquid crystals (DLCs) are potential candidates, where quasi-1D self-assembly affords a charge-transport channel along their columnar axis. This work shows a molecular design strategy by utilizing anthraquinone as the primary motif, surrounded by ester functionalized tri-alkoxy phenyl units to develop room-temperature DLCs (1.

Enhancing Hole Transport and Autonomous Healing Properties of Supramolecular Columns in Unsymmetrical Discotics.

Designing smart autonomous healing soft materials is crucial to attaining cost-efficiency and optimal performance in organic semiconductors. In this context, we design an unsymmetrical thiophene-fused phenazine (TFP)-based discotic liquid crystal (DLC) with the goal of creating an active organic semiconductor that encompasses favorable attributes, such as polarizability, mobility, and processability. Aligned with our objective, we successfully synthesized two unsymmetrical TFP core-based DLCs by linking alkyl chains of variable lengths at the periphery through a coupling reaction.

High Electrical Conductivity and Hole Transport in an Insightfully Engineered Columnar Liquid Crystal for Solution-Processable Nanoelectronics.

Discotic liquid crystals (DLCs) are widely acknowledged as a class of organic semiconductors that can harmonize charge carrier mobility and device processability through supramolecular self-assembly. In spite of circumventing such a major challenge in fabricating low-cost charge transport layers, DLC-based hole transport layers (HTLs) have remained elusive in modern organo-electronics. In this work, a minimalistic design strategy is envisioned to effectuate a cyanovinylene-integrated pyrene-based discotic liquid crystal (PY-DLC) with a room-temperature columnar hexagonal mesophase and narrow bandgap for efficient semiconducting behavior.

Tailoring Chiral Discotic Liquid Crystals: Mesophase Engineering through Alternative Approaches and Chain Lengths.

Hydrogen (H)-bonding is crucial in constructing superstructures in chemical (such as chiral discotic liquid crystals (DLCs)) as well as in biological systems due to its specific and directional nature. In this context, we achieved the successful synthesis of two branches of heptazine-based H-bonded complexes using distinct strategies. Hpz*-Es-C , we incorporated chiral alkyl tails (Hpz-chiral) onto the central C symmetric heptazine core, connected to achiral benzoic acid derivatives (Es-C acid) through H-bonding.

Solution-processable organic light-emitting diodes utilizing electroluminescent perylene tetraester-based columnar liquid crystals.

Herein, we reveal a homologous series of liquid crystals involving perylene tetraesters as the core connected to the four trialkoxyphenyl units at the periphery using the triazole moiety as the linker. A thorough analysis using differential scanning calorimetry, polarized optical microscopy, and small- and wide-angle X-ray scattering studies confirm that all the mesogens 1a-c hold a stable enantiotropic columnar mesophase. Suitable molecular orbital levels and excellent material photophysical and thermal properties encouraged the study of their electroluminescent properties.

Observation of "de Vries-like" properties in bent-core molecules.

"de Vries" liquid crystals, defined by a maximum layer shrinkage of ≤1% from the smectic A to C phase transition, are an integral component of ferroelectric liquid crystal (FLC) displays. Bona fide de Vries materials described in the literature are primarily perfluorinated, polysiloxane and polysilane-terminated rod-like (or calamitic) LCs. Herein, for the first time, we report a series of newly designed achiral unsymmetrical bent-core molecules with terminal alkoxy chains exhibiting similar properties to "de Vries" LCs.

Correction: Luminescent columnar discotics as highly efficient emitters in pure deep-blue OLEDs with an external quantum efficiency of 4.7.

Correction for 'Luminescent columnar discotics as highly efficient emitters in pure deep-blue OLEDs with an external quantum efficiency of 4.7%' by Joydip De , , 2022, DOI: 10.1039/d1sm01558c.

Luminescent columnar discotics as highly efficient emitters in pure deep-blue OLEDs with an external quantum efficiency of 4.7.

Development of materials that serve as efficient blue emitters in solution-processable OLEDs is challenging. In this study, we report three derivatives of -symmetric 1,3,5-tris(thien-2-yl)benzene-based highly luminescent room temperature columnar discotic liquid crystals (DLCs) suitable as solid-state emitters in OLED devices. When employed in solution-processed OLEDs, one of the derivatives having the highest photoluminescence quantum yield exhibited a maximum EQE of 4.

Molecular Engineering for the Development of a Discotic Nematic Mesophase and Solid-State Emitter in Deep-Blue OLEDs.

A unique strategy for the attainment of a discotic nematic (N) mesophase is reported consisting of a central benzene core to which are attached two 4-alkylphenyl and two 4-pentylbiphenyl moieties diagonally via alkynyl linkers. The rotational nature and incompatibility of unequal phenylethynyl units led to the disruption of π-π interactions within cores that aids to the realization of N phase and favors high solid-state emission. When used in OLEDs, compounds act as an efficient solid-state pure deep-blue emitter with Commission Internationale de L'Eclairage (CIE) coordinates of (0.

Luminescent Conductive Columnar π-Gelators for Fe(II) Sensing and Bio-Imaging Applications.

The high demand and scarcity of luminescent, photoconductive, and transparent gels necessitate its finding as they are potential components in photonic devices such as solar cell concentrators where optical losses via scattering and reabsorption require to be minimized. In this direction, we have reported highly transparent, blue luminescent as well as photoconductive gels exhibiting the hole mobility of 10 cm/V s at ambient temperature as investigated by the time-of-flight technique. The -driven self-standing supergels were formed using triazole-modified phenylene-vinylene derivatives as gelators in a nonpolar solvent.

AIE-active mechanoluminescent discotic liquid crystals for applications in OLEDs and bio-imaging.

A multifunctional molecular design of fluorescent discotic liquid crystal (DLC) consisting of a tetraphenylethylene core is reported, which is found to serve as an excellent solid-state emitter in OLED devices with EQE of 4.4% and tunable mechanochromism. X-ray diffraction studies unveiled that change in supramolecular self-assembly is the physical origin of mechanochromism.

High hole mobility in room temperature discotic liquid crystalline tetrathienoanthracenes.

Tetrathienoanthracene (TTA), a new discotic core fragment, is explored that shows a remarkably high hole mobility (μh) of 4.22 cm2 V-1 s-1 at room temperature when used in space-charge limited current (SCLC) devices. Strong co-facial interactions (π-π, SS) among TTA cores along with a high tendency of the derivative to align homeotropically in the columnar mesophase over a large area in SCLC cells contributed to the top-class charge carrier mobility.

Effect of adsorbed polyelectrolytes on the interactions and elasticity of charged surfactant bilayers.

We present studies on the structure of complexes of the cationic, bilayer-forming surfactant, didodecyldimethylammonium bromide (DDAB), and the anionic polyelectrolyte sodium polyacrylate (PAANa). In the presence of uncomplexed polyelectrolyte in the coexisting aqueous solution, these complexes are found to exhibit a swelling transition followed by a deswelling transition on increasing the salt concentration. Lamellar structures with low periodicities occur at both low and high salt concentrations, which are stabilized by polymer bridging and van der Waals attraction, respectively.

High Hole Mobility and Efficient Ambipolar Charge Transport in Heterocoronene-Based Ordered Columnar Discotics.

Heterocoronene, a new redox-active core fragment, is utilized for the synthesis of room-temperature columnar discotic liquid crystals (DLCs). Three wedge-shaped side chains having different lengths of alkyl tails are introduced at the periphery of the heterocoronene core to prepare three kinds of discotic molecules, (R = CH), (R = CH), and (R = CH). X-ray diffraction (XRD) analysis confirmed the packing variation in the columnar lattices regulated by alkyl chains of discrete length and steric bulk.

Polar Switching and Cybotactic Nematic Ordering in 1,3,4-Thiadiazole-Based Short-Core Hockey Stick-Shaped Fluorescent Liquid Crystals.

We report here the synthesis and thermotropic properties of novel short-core hockey stick-shaped liquid crystalline molecules based on the 1,3,4-thiadiazole core. Polar switching behavior is observed in the cybotactic nematic and smectic mesophases for the bent-core thiadiazole derivatives. The presence of the lateral methoxy moiety in the outer phenyl ring of the four-ring molecules facilitates the formation of spontaneous ordering in the nematic phase observed via X-ray diffraction measurements.

Structural Understanding, Photoswitchability, and Supergelation of a New Class of Four Ring-Based Bent-Shaped Liquid Crystal.

Herein, we report a new type of azobenzene-based unsymmetrical bent-core molecules exhibiting photoswitchability in the liquid crystalline state, solid state, and solution state and in mixture upon UV irradiation and intense visible light. The compounds exhibited solid-state photochromism upon exposure to UV light, whereas in liquid crystalline state, reversible phase transitions were observed via both UV irradiation and intense visible light exposure. Crystal structure analysis reveals the basic structural understanding such as nonplanar bent molecular shape, antiparallel arrangement of the polar bent molecules, intra- and intermolecular hydrogen bonding, and different π-π interactions and interdigitation of long alkyl chains.

Room-Temperature Columnar Liquid Crystals as Efficient Pure Deep-Blue Emitters in Organic Light-Emitting Diodes with an External Quantum Efficiency of 4.0.

A novel design of aggregation-induced emission (AIE) active columnar (Col) luminomesogens is reported, and they are demonstrated to act as highly efficient deep-blue emitters in organic light-emitting diodes (OLEDs). All derivatives exhibit Col liquid crystalline (LC) behavior at room temperature over a wide temperature range and desirable alignment properties, which is very important in using them as materials for organic electronic devices. These new AIE active luminomesogens were found to act as highly efficient emitters in OLEDs and unveiled a maximum external quantum efficiency of 4.

Reversibly photoswitchable alkoxy azobenzenes connected benzenetricarboxamide discotic liquid crystals with perpetual long range columnar assembly.

Liquid crystals (LCs) with photoswitchable groups are very interesting owing to their dual applications. In this regard, we report the synthesis of long chain alkoxy azobenzene incorporated benzenetricarboxamides 7a-c based room temperature columnar LCs. Apart from the light induced isomerization in the solution phase, the salient feature of these systems is the reversible photoisomerization even in the bulk state with perpetual columnar self-assembly at room temperature.

Hydrogen-bond mediated columnar liquid crystalline assemblies of C-symmetric heptazine derivatives at ambient temperature.

A new class of hydrogen (H) bonded fluorescent liquid crystals (FLCs) based on a newly discovered s-heptazine fluorophore discotic component have been synthesized. The tendency of the s-heptazine core to form H-bonded LCs has been explored for the first time. Interestingly, the pure heptazine derivatives (non-mesomorphic) on complexation with tri-alkoxy benzoic acids exhibit enantiotropic columnar mesomorphism over a wide range of temperatures including room temperature.

Phase Behavior of a New Class of Anthraquinone-Based Discotic Liquid Crystals.

Five novel columnar liquid crystalline compounds (4.1-4.5) consisting of a central anthraquinone core carrying four alkoxy chains (R = n-CH, n-CH, n-CH, n-CH, and 3,7-dimethyl octyl) with two diagonally opposite 1-ethynyl-4-pentylbenzene units were synthesized, and their phase transitions were investigated between changes in the molecular structure and their self-assembly into the columnar mesophases.

Heptazine: an Electron-Deficient Fluorescent Core for Discotic Liquid Crystals.

Herein, room-temperature discotic liquid crystals based on heptazine, an electron deficient central core, are reported for the first time. Mesomorphic behaviors of the materials are also investigated. Supramolecular assembly of the mesophase derivatives were confirmed by X-ray scattering experiments.

TNF Induced Switching of Columnar Rectangular to Hexagonal Assemblies in a New Class of Triphenylene-Based Room Temperature Discotic Liquid Crystals.

A straightforward synthesis of triphenylene-based oligomeric systems that self-organize into room temperature columnar structures is presented. The compounds with longer spacer length (m = 10 and 12) exhibit columnar rectangular (Col) mesophase whereas the compound with m = 8 exists in glassy Col state. Interestingly, the Col self-assembly of these compounds switches to columnar hexagonal (Col) on doping the compounds with 2,4,7-trinitrofluorenone (TNF).

Room-Temperature Columnar Nematic and Soft Crystalline Columnar Assemblies of a New Series of Perylene-Centred Disc Tetramers.

Three new oligomeric perylene (PE) tetraester derivatives, consisting of a PE-based core with four pentaalkynylbenzene units attached through flexible alkyl spacers, are reported. These derivatives were investigated for their mesomorphic properties and thermal, photophysical, and electrochemical behaviour. Small- (SAXS) and wide-angle X-ray scattering (WAXS) studies were performed to deduce the exact nature of the phases.