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The unique four-level photocycle characteristics of excited-state intramolecular proton transfer (ESIPT) materials enable population inversion and large spectral separation between absorption and emission through their respective enol and keto forms. This leads to minimal or no self-absorption losses, a favorable feature in acting as an optical gain medium. While conventional ESIPT materials with an enol-keto tautomerism process are widely known, zwitterionic ESIPT materials, particularly those with high photoluminescence, are scarce. Facilitated by the synthesis and characterization of a new family of 2-hydroxyphenyl benzothiazole (HBT) with fluorene substituents

Structural direction of hydrogen-bonded thienylenevinylenes reveals that self-assembled to 1D structures exhibit enhanced photoconductivity and charge carrier mobility when compared to 2D sheets.

In this work, white light emission from the blend of a hole transport material, 4,4′-cyclohexylidene bis[N,N-bis(4-methylphenyl)benzenamine] (TAPC), and an electron transport material, 2,2′,2″-(1,3...

Excited state properties such as emission, exciton transport, electron transfer, etc., are strongly dependent on the shape, size and molecular arrangement of chromophore based supramolecular architectures. Herein, we demonstrate creation and control of distinct supramolecular energy landscapes for the reversible control of the excited-state emission processes through cascade energy transfer in chromophore assemblies, facilitated by an unprecedented solvent effect. In methylcyclohexane, a tailor-made Y-shaped BODIPY derivative self-assembles to form an unusual spherical architecture of 400-1200 nm size, which exhibits a single emission at 540 nm upon 475 nm excitation through a normal excitation deactivation process. However, in n-decane, the same BODIPY derivative forms two-dimensional supramolecular sheets, exhibiting multiple emission peaks at 540, 610, 650, 725 and 790 nm with 475 nm excitation due to cascade energy transfer. Further control on the morphology and excitation energy transfer is possible with variable solvent composition and ultrasound stimulation, resulting in enhanced near-infrared emission with an overall pseudo Stokes shift of 7105 cm-1 .

Diels-Alder photocycloaddition, a well-known textbook reaction, has not been explored in materials chemistry. Herein we describe how this classical photochemistry can be used to modulate the lower critical solution temperature (LCST) of a molecular π-system, which can further be exploited for the controlled transmission of solar radiation for the management of indoor heat and light. An amphiphilic anthracene derivative 9-PA-1 exhibited LCST behavior at 27-32 °C with a reversible transition from a transparent to an opaque phase in water (1-5 mM). Irradiation of a toluene solution of 9-PA-1 with 365 nm light resulted in a [4+2] photocycloadduct 9-PA-2, which exhibited a modulated LCST behavior at 25-27 °C, at a concentration as low as 6 μM. The photocycloaddition of 9-PA-1 was significantly retarded in water, making it a stable candidate for the design of sustainable smart windows. We also demonstrated 100 cm

Volumetric capacitance is a more critical performance parameter for rechargeable power supply in lightweight and microelectronic devices as compared to gravimetric capacitance in larger devices. To this end, we report three electrochromic metallopolymer-based electrode materials containing Fe

Dye-sensitized solar cells (DSCs) have proven to be one of the best photovoltaic approaches for harnessing indoor/artificial light. Herein, we report two new molecularly engineered, cost-effective, metal-free, carbazole-based D–π–A sensitizers (YK 8 and YK 9) by judiciously varying their π-spacers, which are suitable for indoor photovoltaic applications. Using YK 8, we achieved an efficiency of 28.7% under standard 1000 lux Osram 14 W T2 cool day light fluorescent tube illumination with a power output of 68.88 μW cm−2 and 30.24% with a power output of 108.85 μW cm−2 under a higher illumination intensity of 1500 lux without co-sensitizers using iodide/triiodide electrolyte. With a small footprint/active area of 1.24 cm2, we could power a temperature sensor completely autonomously at a low light intensity of 500 lux, displaying the potential of these indoor photovoltaic devices to serve as energy sources for low-power sensors and actuators on the Internet of Things (IoT) network, reducing the dependence on batteries and leading to a smaller carbon footprint. The role of the π-spacer and its influence on recombination and device performance were explored via extensive interfacial studies.

Temperature is often not considered as a precision stimulus for artificial chemical systems in contrast to the host-guest interactions related to many natural processes. Similarly, mimicking multi-state volatile memory operations using a single molecular system with temperature as a precision stimulus is highly laborious. Here we demonstrate how a mixture of iron(II) chloride and bipyridine can be used as a reversible color-to-colorless thermochromic switch and logic operators. The generality of the approach was illustrated using CoII and NiII salts that resulted in color-to-color transitions. DMSO gels of these systems, exhibited reversible opaque-transparency switching. More importantly, optically readable multi-state volatile memory with temperature as a precision input has been demonstrated. The stored data is volatile and is lost instantaneously upon withdrawal or change of temperature. Simultaneous read-out at multiple wavelengths results in single-input/multi-output sequential logic operations such as data accumulators (counters) leading to volatile memory states. The present system provides access to thermoresponsive materials wherein temperature can be used as a precision stimulus.

Single-walled carbon nanotubes (SWNTs) are incorporated in different device configurations such as chemiresistors and field-effect transistors (FETs) as a sensing element for the fabrication of highly sensitive and specific biochemical sensors. For this purpose, sorting and aligning of semiconducting SWNTs between the electrodes is advantageous. In this work, a silicon shadow mask fabricated using conventional semiconductor processes and silicon bulk micromachining was used to make metal contacts over SWNTs with a minimum feature of 1 μm gap between the electrodes. The developed silicon shadow mask-based metal contact patterning process is cost-effective and free from photoresist (PR) chemical coatings and thermal processing. After a detailed investigation, sodium dodecyl sulfate (SDS), an anionic surfactant, along with ultrasonication process, was found to be effective for the removal of unclamped and metallic SWNTs, resulting in aligned and clamped semiconducting SWNTs between the electrodes. The presence of aligned semiconducting SWNTs was confirmed using atomic force microscopy (AFM), field emission scanning electron microscopy (FESEM), and Raman spectroscopy techniques. The fabricated devices were tested for nitrogen dioxide (NO2) gas sensing as a test case. The sensitivity enhancement of ∼21 to 76% in the 20-80 ppm NO2 concentration range has been observed in the case of aligned semiconducting SWNT devices compared to the random network SWNT-based sensors.

Exciton interactions are not only observed in assembled molecules but also in compounds with multiple chromophores referred to as superchromophores. We have developed isomeric bis-squaraine dyes as superchromophores in which two squaraine chromophores are fused onto the isomeric benzodipyrrole skeleton so as to regulate conformations and to reduce distances between two chromophores. The dyes with benzo[1,2-b:3,4-b']dipyrrole and benzo[1,2-b:5,4-b']dipyrrole moieties exhibited split electronic absorption originated from the intramolecular exciton interaction. The intensity of the split absorption bands varies in correlation with the orientation of chromophores. The isomeric dye with benzo[1,2-b:4,5-b']dipyrrole moiety exhibited a near-infrared absorption associated with the resonance throughout two chromophores. Their electrochemical and spectroelectrochemical properties are distinct from those of monomeric dyes owing to electronic interactions between the two chromophores. Thus, the structural isomerism of the central skeleton significantly affects their optical properties as well as their electrochemical properties.

Efficient fluorophores with easy synthetic routes and fast responses are of great importance in clinical diagnostics. Herein, we report a new, rigid pentacyclic pyrylium fluorophore, PS-OMe, synthesised in a single step by a modified Vilsmeier–Haack reaction. Insights into the reaction mechanism facilitated a new reaction protocol for the efficient synthesis of PS-OMe which upon demethylation resulted in a “turn-on” pH sensor, PS-OH. This new fluorescent probe has been successfully used to monitor intracellular acidification at physiological pH. From the fluorescence image analysis, we were able to quantify the intracellular dynamic pH change during apoptosis. This new pH probe is a potential chemical tool for screening, drug discovery and dose determination in cancer therapy., A modified Vilsmeier–Haack reaction resulted in the synthesis of a pyrylium based turn-on fluorescent pH probe. The probe can monitor minute acidification and dynamic pH variation in cells during apoptosis with therapeutic chemo drugs.

Poor control on the exfoliation of covalent organic frameworks (COFs) remains a disadvantage for their application as two-dimensional nanosheets. An equally important problem is the reversible control at the available surface charges on COFs. Herein, a strategy for the reversible exfoliation, re-stacking, and surface-charge control of a propidium iodide based ionic covalent organic framework, PI-TFP, using cucurbit[7]uril (CB[7]) induced molecular recognition, is reported. The surface charge on PI-TFP facilitates its initial self-exfoliation. However, complexation with CB[7] resulted in re-stacking with concomitant decrease in zeta potential from +28±3.0 to +0.004±0.003 mV. Addition of 1-adamantylamine hydrochloride (AD) facilitates decomplexation of PI-TFP from CB[7], resulting in exfoliation and an increase in zeta potential to +24±3.0 mV. Such control on the exfoliation, re-stacking, and the associated regulation of the surface charge in PI-TFP was exploited for controlling bacterial growth. Thus, the activity of E. coli and S. aureus bacteria obtained with the self-exfoliated PI-TFP could be reversibly controlled by the CB[7]/AD pair.

Diels-Alder photocycloaddition of 9-phenylethynylanthracene results in multiple [4 + 2] and [4 + 4] cycloaddition products in solution, which can be controlled to form specific products under a restricted environment. We have exploited the gel phase of a 9-phenylethynylanthracence derivative as a confined medium to specifically yield the [4 + 2] cycloadduct in >90% yield. The photocycloadduct ( anti-form) exhibited a blue emission with CIE chromaticity of x = 0.16/ y = 0.16. Construction of an organic light emitting device with the photocycloadduct, using a carbazole-based hole transporting host, resulted in white light emission with a CIE chromaticity of x = 0.33/ y = 0.32. This observation not only highlights the use of gel chemistry to achieve the otherwise difficult to obtain photoproducts but also underlines their potential in optoelectronic device fabrication.

The synthesis, characterization, and spectroscopic investigations of a new solution‐processable N‐styrylcarbazole‐linked tetraphenylethylene (TPE) derivative (TPE‐BCzS) are reported, exhibiting green–orange emission. While the material displays weak photoluminescence (PL) in solution with a low PL quantum yield (PLQY of 4 ± 0.2%), significant PL enhancement in neat‐film PLQY (55 ± 8%) is observed. Studies using steady‐state spectroscopy, and femtosecond and nanosecond transient absorption spectroscopy reveal details of the excited‐state dynamics, consisting of the Franck–Condon (FC) state, nonradiative conformational relaxation, and formation and decay of the triplet excited state generated via intersystem crossing (ISC) upon ultrafast photoexcitation. Solution‐processed organic light‐emitting diodes (OLEDs) based on TPE‐BCzS display maximum external quantum efficiencies of 1.8% and 1.7% for neat and blend films (20 wt% in a 4,4′‐bis(N‐carbazolyl)‐1,1′‐biphenyl host), approaching the theoretical efficiency limit for the determined PLQYs of the films. While TPE materials are typically associated with aggregation‐induced emission, it is reported that the enhanced PLQYs in the solid state are due to restriction of structural relaxations in the solid state and not due to the commonly misunderstood aggregation effect.

Designing surface-confined molecular systems capable of expressing changes in functional properties as a result of slight variations in chemical structure under the influence of an external stimulus is of contemporary interest. In this context, we have designed three tetraterpyridine ligands with variations in their core architecture (phenyl vs tetraphenylethynyl vs bithiophene) to create spray-coated electrochromic assemblies of iron(II)-based metallosupramolecular polymer network films on transparent conducting oxide substrates. These assemblies exhibited molecular permeability and spectroelectrochemical properties that are in turn dictated by the ligand structure. Electrochromic films with high coloration efficiencies (up to 1050 cm2/C) and superior optical contrast (up to 76%) with a concomitant color-to-color redox transition were readily achieved. These functional switching elements were integrated into sandwich-type electrochromic cells (CE up to 641 cm2/C) that exhibited high contrast ratios of up to 56%, with attractive ON-OFF ratios, fast switching kinetics, and high operational stability. Every measurable spectroelectrochemical property of the films and devices is an associated function of the ligand structure that coordinates the same metal ion to different extents. While exhibiting a ligand-structure induced differential metal coordination leading to porosity and spectroelectrochemical diversification, these assemblies allow the creation of electrochromic patterns and images by a simple spray-coating technique.

Single-walled carbon nanotubes (SWNTs) are incorporated in different device configurations such as chemiresistors and field-effect transistors (FETs) as a sensing element for the fabrication of highly sensitive and specific biochemical sensors. For this purpose, sorting and aligning of semiconducting SWNTs between the electrodes is advantageous. In this work, a silicon shadow mask fabricated using conventional semiconductor processes and silicon bulk micromachining was used to make metal contacts over SWNTs with a minimum feature of 1 μm gap between the electrodes. The developed silicon shadow mask-based metal contact patterning process is cost-effective and free from photoresist (PR) chemical coatings and thermal processing. After a detailed investigation, sodium dodecyl sulfate (SDS), an anionic surfactant, along with ultrasonication process, was found to be effective for the removal of unclamped and metallic SWNTs, resulting in aligned and clamped semiconducting SWNTs between the electrodes. The presence of aligned semiconducting SWNTs was confirmed using atomic force microscopy (AFM), field emission scanning electron microscopy (FESEM), and Raman spectroscopy techniques. The fabricated devices were tested for nitrogen dioxide (NO

Three metal-free organic D-π-A dyes with benzothieno[3,2-b]indole as electron donor, cyanoacrylic acid as both electron acceptor and anchoring group with benzene (BID-1), thiophene (BID-2) and furan (BID-3) as π-spacers were designed and synthesized for application in dye-sensitized solar cells (DSSCs). A planar and electron-rich heterocycle such as benzothieno[3,2-b]indole offers better backbone rigidity and improves charge transport properties in comparison to indolo[3,2-b]indole donor, previously reported from our group. Additionally, we synthesized a benzothieno[3,2-b]indole donor grafted with longer alkyl chains which efficiently prevented the approach of oxidized species in the electrolyte coming closer to semiconductor thereby arresting recombination. A power conversion efficiency of 4.11 % was achieved for dye-sensitized solar cells based on the furan π-spacer benzothieno[3,2-b]indole dye BID-3 in comparison to the corresponding indolo[3,2-b]indole dye (IID-3) having an efficiency of 1.71 %. Detailed interfacial electrical measurements along with theoretical calculations disclosed the mechanism of back electron transfer and improvement in photovoltaic performance with respect to variation in both donor and π-spacer.

Mechanochromism is a stress induced perturbation of electronic property in molecular materials. It is shown here that the presence of a branched chiral chain facilitates mechanochromic response in a molecular assembly as illustrated with a chiral oligo(p-phenylenevinylene) derived π-gelator (OPVC). OPVC exhibits a reversible mechanochromism while the analogous achiral derivative (OPVA) having a linear side chain does not, as established from the fluorescence and circular dichroism (CD) studies. The helically twisted chromophore packing in OPVC allows mechanical reorganization of the self-assembly and the associated fluorescence intensity variation at different wavelength positions in the broad emission spectrum, resulting in a perturbation in the colour ratio leading to the observed mechanochromic emission color change. This exciting new finding may have wide ranging implications in the design of stimuli responsive molecular materials with reversible optical properties.

Molecules and materials derived from self-assembled extended π-systems have strong and reversible optical properties, which can be modulated with external stimuli such as temperature, mechanical stress, ions, the polarity of the medium, and so on. In many cases, absorption and emission responses of self-assembled supramolecular π-systems are manifested several times higher when compared with the individual molecular building blocks. These properties of molecular assemblies encourage scientists to have a deeper understanding of their design to explore them for suitable optoelectronic applications. Therefore, it is important to bring in highly responsive optical features in π-systems, for which it is necessary to modify their structures by varying the conjugation length and by introducing donor-acceptor functional groups. Using noncovalent forces, π-systems can be put together to form assemblies of different shapes and sizes with varied optical band gaps through controlling intermolecular electronic interactions. In addition, using directional forces, it is possible to bring anisotropy to the self-assembled nanostructures, facilitating efficient exciton migration, resulting in the modulation of optical and electron-transport properties. In this Account, we mainly summarize our findings with optically tunable self-assemblies of extended π-systems such as

Comprehensive profiling of multiple protein targets plays a critical role in deeper understanding of specific disease conditions associated with high heterogeneity and complexity. Herein, we present the design and fabrication of smart programmable nanoarchitectures, which could integrate clinically relevant diagnostic modalities for the multiplexed detection of most prevalent panel of disease biomarkers present in lung cancer. The multiplex nanoprobes were prepared by attaching dual-functional Raman-active fluorogens onto spherical gold nanoparticles through a peptide linker, Phe-Lys-Cys (FKC), which is engineered with a cathepsin B (cathB) enzyme cleavage site. The presence of cathB induces the scission of FKC upon homing into the cancer cells, resulting in the release of the initially latent fluorophores with a concomitant quenching of the surface-enhanced Raman signal intensity, thereby realizing an on-off switching between the fluorescence and Raman modalities. The enzyme-triggered switchable nanoprobes were utilized for the simultaneous detection of pathologically relevant lung cancer targets by tethering with specific antibody units. The multiplex-targeted multicolor coded detection capability of the antitags was successfully developed as a valid protein screening methodology, which can address the unmet challenges in the conventional clinical scenario for the precise and early diagnosis of lung cancer.

V-shaped squaraine dyes with carbazole cores in the center and indolenine groups at the end were designed to broaden the light-harvesting range of dye-sensitized solar cells (DSSCs) by taking advan...

Organelle-targeted photosensitizers (PSs) having luminescence properties are potential theranostic agents for simultaneous luminescence imaging and photodynamic therapy. Herein, we report a water-soluble luminescent cyclometalated IrIII complex, Ir-Bp-Ly, as a lysosome-targeted theranostic probe. Ir-Bp-Ly exhibits exceptional photophysical properties, with good triplet-state quantum yield (0.90), singlet oxygen generation quantum yield (0.71 at pH 4), and long lifetime (1.47 μs). Interestingly, Ir-Bp-Ly localizes mostly in lysosomes due to the presence of morpholine units, suggesting its potential use as a lyso-tracker. Ir-Bp-Ly displays a notable PDT effect in C6 glioma cells, efficiently generating reactive oxygen species owing to close proximity between the energy levels of its triplet state and those of molecular oxygen (3 O2 ). The mechanism of cell death has been studied through caspase-3/7 and flow cytometry analyses, which clearly established the apoptotic pathway.

Ionic covalent organic nanosheets (iCONs), a member of the two-dimensional (2D) nanomaterials family, offer a unique functional platform for a wide range of applications. Herein, we explore the potential of an ethidium bromide (EB)-based covalent organic framework (EB-TFP) that self-exfoliates in water resulting in 2D ionic covalent organic nanosheets (EB-TFP-iCONs) for the selective detection of double-stranded DNA (dsDNA). In an aqueous medium, the self-exfoliated EB-TFP-iCONs reassemble in the presence of dsDNA resulting in hybrid EB-TFP-iCONs-DNA crystalline nanosheets with enhanced fluorescence at 600 nm. Detailed steady-state and time-resolved emission studies revealed that the reassembly phenomenon was highly selective for dsDNA when compared to single-stranded DNA (ssDNA), which allowed us to use the EB-TFP-iCONs as a 2D fluorescent platform for the label-free detection of complementary DNA strands.

Rational understanding of the structural features involving different noncovalent interactions is necessary to design a liquid crystal (LC) or an organogelator. Herein, we report the effect of the number and positions of alkoxy chains on the self-assembly induced physical properties of a few π-conjugated molecules. For this purpose, we designed and synthesized three C3-symmetrical molecules based on oligo(p-phenylenevinylene), C3OPV1–3. The self-assembly properties of these molecules are studied in the solid and solution states. All of the three molecules follow the isodesmic self-assembly pathway. Upon cooling from isotropic melt, C3OPV1 having nine alkoxy chains (−OC12H25) formed a columnar phase with two-dimensional rectangular lattice and retained the LC phase even at room temperature. Interestingly, when one of the −OC12H25 groups from each of the end benzene rings is knocked out, the resultant molecule, C3OPV2 lost the LC property, however, transformed as a gelator in toluene and n-decane. Surprisin...

Self-assembled synthetic hybrid materials are an important class of artificial materials with potential applications in various fields ranging from optoelectronics to medicine. The noncovalent interactions involved in the self-assembly process offer a facile way to create hybrid materials with unique and interesting properties. In this context, self-assembled hybrid materials based on carbon nanotubes (CNTs), graphene, and graphene derivatives such as graphene oxide (GO) and reduced graphene oxide (RGO) are of particular significance. These composites are solution processable, generally exhibit enhanced electrical, mechanical, and chemical properties, and find applications in the fields of light harvesting, energy storage, optoelectronics, sensors, etc. Herein, we present a brief summary of recent developments in the area of self-assembled functional hybrid materials comprising one-dimensional (1D) or two-dimensional (2D) carbon allotropes and synthetic π-systems such as aromatic molecules, gelators, and polymers. Functionalizing carbon allotropes with aromatic molecules is a promising way to realize hybrid materials with various applications. Carbon nanomaterials, such as two-dimensional graphene and one-dimensional carbon nanotubes, have already started to find uses in electronic and optoelectronic applications. Hybrid materials that combine these carbon nanostructures with small aromatic molecules or polymers can extend the range of applications further still. Ayyappanpillai Ajayaghosh from the CSIR-National Institute for Interdisciplinary Science and Technology and co-workers have reviewed the various approaches developed to combine these carbon allotropes with organic materials and thus create even more functional materials. They give an overview of the various solution-processed self-assembly methods used to create functional hybrid allotropes of carbon and their potential uses in novel light-harvesting systems, solar cells and organic field-effect transistors. Exploration of noncovalent interactions of such as H-bonding, p-stacking and van der Waals forces to the design of hybrid materials of 1D or 2D carbon allotropes and synthetic p-systems such as aromatic small molecules, gelators and polymers for various applications ranging from materials to biology are discussed.

Efficient optical outcoupling from organic light emitting diodes (OLEDs) is an important challenge in solid state lighting technology. In this work, the effect of an external light extraction layer, prepared using polydimethylsiloxane (PDMS) and zinc oxide (ZnO) nanoparticles, was studied on the performance of red, green, blue and white OLEDs. The self-standing flexible film can effectively address the loss modes at the substrate-air interface. With the application of the layer, a maximum enhancement of about 80% in light outcoupling was observed in white OLEDs. Monochrome OLEDs also showed appreciable enhancement in emission with green having the highest improvement (102%), followed by red (56%) and blue (35%). Finite-difference time-domain (FDTD) simulations were performed for elucidating the mechanism behind the improvement in light extraction due to nanoparticle scattering layer. Total-Field Scattered-Field (TFSF) source was used to simulate the scattering cross-section for different wavelengths. Reduced Fresnel reflections at the air-glass interface and advantageous Mie scattering by ZnO nanoparticles seem to increase the optical outcoupling. This film could be a potential candidate for light extraction in OLEDs because of its facile fabrication, economical precursors, and adaptability to flexible substrates and absence of any possible optical artefacts to the emission.

Self-assembly is a viable approach to create soft functional materials with architectural diversity and property variations. Among the large number of different chromophores used, borondipyrromethene (Bodipy) dyes find a unique space because of their promising photophysical properties such as high molar absorptivity, fluorescent quantum yield and excellent photostability along with the associated synthetic ease. Recently, research on Bodipy dyes has experienced a surge of activities in view of favorable self-assembling properties. In this review, recent developments in self-assembled Bodipy dyes and their significance in various applications are discussed.

Functional differences between superhydrophobic surfaces, such as lotus leaf and rose petals, are due to the subtle architectural features created by nature. Mimicry of these surfaces with synthetic molecules continues to be fascinating as well as challenging. Herein, we demonstrate how inherently hydrophilic alumina surface can be modified to give two distinct superhydrophobic behaviors. Functionalization of alumina with an organic ligand resulted in a rose-petal-like surface (water pinning) with a contact angle of 145° and a high contact angle hysteresis (±69°). Subsequent interaction of the ligand with Zn2+ resulted in a lotus-leaf-like surface with water rolling behavior owing to high contact angle (165°) and low-contact-angle-hysteresis (±2°). In both cases, coating of an aromatic bis-aldehyde with alkoxy chain substituents was necessary to emulate the nanowaxy cuticular feature of natural superhydrophobic materials.

Higher-order super-helical structures derived from biological molecules are known to evolve through opposite coiling of the initial helical fibers, as seen in collagen protein. A similar phenomenon is observed in a π-system self-assembly of chiral oligo(phenyleneethylene) derivatives (S)-1 and (R)-1 that explains the unequal formation of both left- and right-handed helices from molecule having a specific chiral center. Concentration- and temperature-dependent circular dichroism (CD) and UV/Vis spectroscopic studies revealed that the initial formation of helical aggregates is in accordance with the molecular chirality. At the next level of hierarchical self-assembly, coiling of the fibers occurs with opposite handedness, thereby superseding the command of the molecular chirality. This was confirmed by solvent-dependent decoiling of super-helical structures and concentration-dependent morphological analysis.

Cyano-substituted p-phenylenevinylene (R-1) aggregates exhibiting fluorescence and Raman spectroscopic responses towards CO2 are described. The aggregation-induced emission (AIE) as well as the aggregation-enhanced Raman scattering (AERS) of R-1 in aqueous conditions was reduced in the presence of a small amount of CO2, which enabled its easy and fast bimodal detection in different analytical samples.

Supramolecular polymerization of donor-acceptor type molecules leads to mixed or self-sorted assemblies depending on the donor-acceptor strength and extent of noncovalent interactions between the components. Herein, we discuss how competing hydrogen bonding motifs control the supramolecular polymerization pathway of a two-component molecular π-system of oligo(p-phenylenevinylene) (OPV-B and OPV-P) donors and perylene bisimide (PBI-B and PBI-A) acceptors. It is shown that among the four different binary combinations (M1-M4) studied, the carboxylic acid/pyridine heterosystem (1 : 2 molar ratio) in M4 favors the coassembled donor-acceptor stacks with a distinct morphology, whose aggregation pathways in toluene/THF (v/v : 9/1) is different from that of the individual components. The nanoscopic molecular arrangement of OPV-P driven by PBI-A in M4 was found to influence the bulk properties such as, morphology, thermomechanical stability and electrical conductivity. For example, the G' and G'' values of M4 is an order of the magnitude higher and exhibited a four-probe electrical conductivity (11.93 Scm-1 ) higher than that of its individual components. Thus, hydrogen-bond intervention is a powerful strategy to control the supramolecular polymerization of two-component donor-acceptor π-systems.

The making of hybrid materials from polymers and self-assembled systems may open up new horizons for imparting new properties to usual polymers without recourse to chemistry. Here it is again shown...

We report an unprecedented strategy to generate and amplify near-infrared (NIR) emission in an organic chromophore by mechanical stress or gelation pathways. A greenish-yellow emitting film of π-extended Bodipy-1, obtained from n-decane, became orange-red upon mechanical shearing, with a 15-fold enhancement in NIR emission at 738 nm. Alternatively, a DMSO gel of Bodipy-1 exhibited a 7-fold enhancement in NIR emission at 748 nm with a change in emission color from yellow to orange-red upon drying. The reason for the amplified NIR emission in both cases is established from the difference in chromophore packing, by single crystal analysis of a model compound (Bodipy-2), which also exhibited a near identical emission spectrum with red to NIR emission (742 nm). Comparison of the emission features and WAXS and FT-IR data of the sheared n-decane film and the DMSO xerogel with the single crystal data supports a head-to-tail slipped arrangement driven by the N–H⋯F–B bonding in the sheared or xerogel states, which facilitates strong exciton coupling and the resultant NIR emission.

Among several methodologies to improve the solution processing of graphene-based materials, noncovalent functionalization has been considered as the simplest and nondestructive method. Herein, we show that molecular self-assembly process can be used as a useful tool to exfoliate reduced graphene oxide (RGO), resulting in hybrid materials with improved physical properties. Upon interacting with a π-gelator, the dispersing ability of the RGO increased significantly in most of nonpolar and polar aprotic solvents when compared to the bare one. The amount of RGO dispersed was 1.7–1.8 mg mL–1 in solvents such as toluene, o-dichlorobenzene (ODCB) and tetrahydrofuran (THF). Morphological studies revealed that aggregation of π-gelator over RGO helps to exfoliate graphene layers to remain as individual sheets with higher surface area. Experimental studies revealed enhanced surface area (250 m2 g–1) and better conductivity (3.7 S m–1) of the hybrid materials with 30% of RGO content resulting in excellent electrochem...

Three-component random copolymers having different ratios of [1]benzothieno[3,2-b]benzothiophene (BTBT) and diketopyrrolopyrrole (DPP) units were synthesized, and their application in organic field effect transistors (OFET) has been discussed. These low band gap polymers exhibit p-type semiconducting properties, and it has been observed that increase in the percentage composition of the fused chalcogenophene (BTBT) in the polymer backbone significantly improves the charge carrier mobility (μh) up to 2.47 cm2 V–1 s–1. The GIXRD technique and AFM have been used to explain the influence of BTBT on the nature of molecular packing in the polymer thin films. These results unveil the role of the effective conjugation length as well as the intermolecular ordering of the polymer chains on the charge carrier transport in OFET.

π-Gels are a promising class of functional soft materials formed out of short π-conjugated molecules. By utilizing the chemistry of noncovalent interactions, researchers have created a wide range of π-gels that are composed of supramolecular polymers. During the last two decades, supramolecular gel chemistry has been pursued with the hope of developing new materials for applications in, for example, organic electronics, energy harvesting, sensing, and imaging. The high expectations for π-gels were centered mainly around their electronic properties, such as tunable emission, energy transfer, electron transfer, charge transport, and electrical conductivity; such properties are amenable to modulation through size and shape control of molecular assemblies. Although a large number of exciting publications have appeared, a major technological breakthrough is yet to be realized. In this review, we analyze the recent advancements in the area of functional π-gels and their scope in future applications.

Coordination polymers and metal–organic frameworks have attracted immense attention across different fields of science as materials with numerous functional applications. Herein, we report the use of coordination polymers obtained from near-isostructural metal (Mn2+, Fe2+, and Co2+) bipyridine complexes as electrode materials in a symmetric supercapacitor test cell. The variation in the central metal ion (Mn2+ vs. Fe2+ vs. Co2+) in these nearly identical coordination complexes was found to dictate the capacitive performance of the coordination polymers obtained via Pd(II) cross-linking. The central metal ion not only influences the porosity, Brunauer–Emmett–Teller (BET) surface area (6.5 (Mn), 10.4 (Fe), and 29.7 (Co) m2/g), and the areal capacitance, but also the performance parameters such as the cycling stability and charge–discharge kinetics as well as the charge transfer mechanism. A 3:4:5 ratio for the areal capacitance values (9.1 (Mn), 12.2 (Fe), and 15.4 (Co) mF cm−2 at a scan rate of 5 mV/s) corroborates the modulative effect of the metal center. The cycling stabilities of these coordination polymers also followed the same order. At higher current densities (>0.50 mA cm−2), the supercapacitors fabricated from the Mn-coordination polymer were found to charge and discharge at faster rates, whereas those fabricated from Fe- or Co-coordination polymers continued to discharge at similar rates, indicating similar pore volumes for the latter as confirmed by BET surface area measurements. Although the materials used in this study resulted in modest capacitive performance, the possibilities to enhance their surface area and crystallinity is envisaged to result in the development of new, multifunctional non-carbon electrode materials with efficient electrochemical storage characteristics and tunable electro-optical properties.

The very concept of dye and pigment chemistry that was long known to the industrial world underwent a radical revision after the discovery and commercialization of dyes such as mauveine, indigo, and so on. Apart from their conventional role as coloring agents, organic dyes, and pigments have been identified as indispensable sources for high-end technological applications including optical and electronic devices. Simultaneous with the advancement in the supramolecular chemistry of π-conjugated systems and the divergent evolution of organic semiconductor materials, several dyes, and pigments have emerged as potential candidates for contemporary optoelectronic devices. Of all the major pigments, diketopyrrolopyrrole (DPP) better known as the ‘Ferrari Pigment’ and its derivatives have emerged as a major class of organic functional dyes that find varied applications in fields such as industrial pigments, organic solar cells, organic field–effect transistors, and in bioimaging. Since its discovery in 1974 by Farnum and Mehta, DPP-derived dyes gained rapid attention because of its attractive color, synthetic feasibility, ease of functionalization, and tunable optical and electronic properties. The advancement in supramolecular polymerization of DPP-based small molecules and oligomers with directed morphological and electronic features have led to the development of high performing optoelectronic devices. In this review, we highlight the recent developments in the optoelectronic applications of DPP derivatives specifically engineered to form supramolecular polymers.

Organic semiconductors with variable charge carrier polarity are required for optoelectronic applications. Herein, we report the synthesis of three novel diketopyrrolopyrrole (DPP)-based D–A molecules having three different terminal groups (amide, ester, and dicyano) and study their electronic properties. An increase in electron acceptor strength from amide to dicyano leads to a bathochromic shift in absorption. Photoconductivity and field effect transistor (FET) measurements confirmed that a small increase in acceptor strength can result in a large change in the charge transport properties from p-type to n-type. The molecule with an amide group, DPP–amide, exhibited a moderate p-type mobility (1.3 × 10–2 cm2 V–1 s–1), whereas good n-type mobilities were observed for molecules with an ester moiety, DPP–ester (1.5 × 10–2 cm2 V–1 s–1), and with a dicyano group, DPP–DCV (1 × 10–2 cm2 V–1 s–1). The terminal functional group modification approach presented here is a simple and efficient method to alter the cha...