Deciphering pressure-induced nanoarchitectonics in a monolayer of heterocoronene-based discotics at air-water and air-solid interfaces.

Understanding and control of molecular alignment at the nanoscale in self-assembled supramolecular structures is a prerequisite for the subsequent exploitation of molecules in functional devices. Here, we have clarified the surface-pressure induced molecular nanoarchitectures in a monolayer of a heterocoronene-based discotic liquid crystal (DLC) at air-water and air-solid interfaces using surface manometry, real-time Brewster angle microscopy, and real-space atomic force microscopy (AFM). Chloroform-spread DLCs at a concentration of ∼108 µM exhibit floating domains at the air-water interface comprising small aggregates of edge-on stacked molecules interacting via peripheral alkyl chains. Detailed analysis of surface manometry and relaxation measurements reveal that, upon compression, these domains coalesce to form a coherent monolayer which then undergoes irreversible structural transformations via mechanisms such as monolayer loss due to desorption and localized nucleation of defects. AFM images of the films transferred on a hydrophilic substrate reveal that with increasing surface-pressure, the nanoscale structure of the monolayer transforms from randomly oriented nanowires to tightly-packed nanowire domains, and finally to fragmented wire segments which diffuse locally above the film. These results provide a facile method for the preparation of compact, two-dimensional films of ambipolar DLC molecules with a tunable nanoarchitecture which will be crucial for their applications in nanoscale electronic devices.

Thermally Activated and Aggregation-Regulated Excitonic Coupling Enable Emissive High-Lying Triplet Excitons.

Room-temperature phosphorescence (RTP) originating from higher-lying triplet excitons remains a rather rarely documented occurrence for purely organic molecular systems. Here, we report two naphthalene-based RTP luminophores whose phosphorescence emission is enabled by radiative decay of high-lying triplet excitons. In contrast, upon cooling the dominant phosphorescence originates from the lowest-lying triplet excited state, which is manifested by a red-shifted emission. Photophysical and theoretical studies reveal that the unusual RTP results from thermally activated excitonic coupling between different conformations of the compounds. Aggregation-regulated excitonic coupling is observed when increasing the doping concentration of the emitters in poly(methylmethacrylate) (PMMA). Further, the RTP quantum efficiency improves more than 80-fold in 1,3-bis(N-carbazolyl)benzene (mCP) compared to that in PMMA. This design principle offers important insight into triplet excited state dynamics and has been exploited in afterglow-indicating temperature sensing.

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 et al., Soft Matter, 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 C3-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 4.7% and CIE chromaticity of (0.16, 0.05) corresponding to the ultra deep-blue emission. The finding is sufficiently significant in the field of DLC-based deep blue emitters.

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 (ND) 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 ND 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 (CIEx,y) coordinates of (0.16, 0.07).

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 10-3 cm2/V s at ambient temperature as investigated by the time-of-flight technique. The π-driven self-standing supergels were formed using triazole-modified phenylene-vinylene derivatives as gelators in a nonpolar solvent. Different microscopic studies revealed its entangled network of interwoven fibrilar self-assembly and anisotropic order in the gel state. Supramolecular assembly of xerogels, studied by small- and wide-angle X-ray scattering (SAXS/WAXS) suggesting their local columnar hexagonal (Colh) superstructure, is beneficial for conducting gels. Rheological measurements direct the stiffness and robustness of the organogels. In addition, the gelators were developed as a sensing platform for the ultrasensitive detection of Fe(II) ions at ppb level. 1H nuclear magnetic resonance (NMR) titrimetric studies revealed that the interaction of the H-atom of triazole units with Fe(II) is responsible for quenching of blue fluorescence. Also, one of the gelators was successfully applied in bio-imaging using the pollen grains of the Hibiscus rosa-sinensis plant.

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. The luminescent DLC molecule has been shown to act as a highly selective probe for labelling acidic cellular compartments (such as lysosomes) in bio-imaging using HeLa cells.

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.

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, 1 (R = C10H21), 2 (R = C12H25), and 3 (R = C14H29). X-ray diffraction (XRD) analysis confirmed the packing variation in the columnar lattices regulated by alkyl chains of discrete length and steric bulk. When used in space charge limited current devices, compound 1 exhibits a high hole mobility value of 8.84 cm2/V s at ambient temperature, whereas compounds 2 and 3 show efficient ambipolar charge transport behavior with maximum hole (µh) and electron (µe) mobilities of 0.70 and 3.59 cm2/V s, respectively, for compound 3. The mobility values (µh = 8.84 cm2/V s for 1 and µe = 3.59 cm2/V s for 3) are remarkable and the highest ever disclosed for any DLC-based organic semiconductor, promising to deliver a good balance between mobility and processability in devices. The grazing incidence small- and wide-angle X-ray scattering experiments are employed to quantify the extent of alignment in the film state, which correlates with the observed trend of mobility values.

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 4.0% for the first time in Col LCs with Commission International de l'E'clairage coordinates of (0.17, 0.07), which closely matches the National Television System Committee (NTSC) standard, corresponding to pure deep blue color. The detailed supramolecular assembly of the compounds has been characterized by modeling in the mesophase derived from small- and wide-angle X-ray scattering results.

Gold nanoparticle-mediated signal amplification of liquid crystal biosensors for dopamine.

A unique design strategy was developed for the detection of dopamine using a newly synthesized amphiphile containing boronic acid head group at the aqueous-liquid crystal (LC) interface. The optical signal of LC for the detection of dopamine was highly amplified in the presence of functionalized gold nanoparticles.

Hydrogen-bond mediated columnar liquid crystalline assemblies of C3-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. This indicates the strength of the resulting H-bonded complexes. The H-bonded supramolecular complexes were studied through FT-IR, temperature dependent FT-IR and NMR studies and H-D exchange studies, and their thermal behaviour was deduced through polarized optical microscopy (POM), differential scanning calorimetry (DSC) and X-ray diffraction (XRD) studies. Because of the inherently fluorescent pure heptazine derivative, the resulting complexes exhibit fluorescent behaviour in the solution state as well as in the solid state.

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-C6H13, n-C8H17, n-C10H21, n-C12H25, 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. Small and wide-angle X-ray scattering (SAXS/WAXS) studies were performed to deduce the exact nature of the mesophases, and their corresponding electron density maps were derived from the intensities of the peaks observed in the diffraction patterns. A comparison of compounds with different alkoxy chains indicated that the soft crystal columnar rectangular (Crcolrec) phase was stable at lower temperature for the shortest peripheral alkoxy chain (4.1; R = n-C6H13) and was found to exhibit the columnar hexagonal (Colh) phase and then the discotic nematic (ND) phase with increasing temperature. In contrast, increasing the peripheral chain length to n-C8H17 or the branched one (4.2 and 4.5) stabilized the Colh phase at lower temperature and showed the ND phase at higher temperature. Further increase in chain length (4.3 and 4.4; n-C10H21, n-C12H25) demonstrated the formation of the ND phase. Conductivity measurement in the Colh mesophase was found to be almost 10 times higher in magnitude than the corresponding Crcolrec phase. The HOMO-LUMO band gap of all the compounds was found to be in the range from 2.79 to 2.82 eV, which is quite less and comparable with the optical energy band gap.

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. Heptazine-based solid thin films are strong blue light emitters, whereas in the solution state, they are weakly emissive or non-emissive. The band gap energy is found to be low in this class of compounds. Formation of room-temperature mesophases, low band-gap behavior, and strong blue-light emission in the solid state are promising attributes for optoelectronic applications of the materials.

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. To resolve overlapping reflections and facilitate their indexing, grazing-incidence SAXS/WAXS experiments were carried out on oriented thin films on indium tin oxide (ITO)-coated glass substrate. The corresponding electron density maps were derived from the intensities observed in the diffraction pattern. Whereas compounds with shorter alkyl spacers (n=6 and 8) were found to self-organise into soft crystalline columnar assemblies, those with longer spacers (n=10) exhibited a liquid-crystalline columnar nematic mesophase. This is in contrast to previous reports that describe highly symmetric 2D hexagonal and rectangular columnar structures of PE-based mesogens. The morphology of self-assembly was found to transform from soft crystal columnar to nematic columnar phase through simple variation in the number of alkyl spacers. All compounds exhibited excellent fluorescence emission properties with a very good quantum yield and large band gap. Apart from high solubility and good quantum yield, these compounds can serve as standards to measure quantum yields of unknown samples. These compounds also display green luminescence and may find applications for various optoelectronic devices.