Search Results (159)

Organic field-effect transistors (OFETs) require reliable micro- and nanoscale patterning of semiconducting layers, yet conjugated polymers have long been considered incompatible with photolithography due to dissolution and chemical damage from photoresist solvents. Here, we present a photolithography-compatible strategy based on doping-induced solubility conversion (DISC), demonstrated using poly[2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2-b]thiophene] (PBTTT). AuCl₃ doping reversibly modulates the benzoid/quinoid resonance balance, lamellar stacking, and π–π interactions, suppressing solubility during lithographic exposure, while dedoping restores the intrinsic electronic properties. Using this approach, micropatterns with linewidths as small as 2 µm were fabricated in diverse geometries—including line arrays, concentric rings, dot arrays, and curved channels—with high fidelity; quantitative analysis of dot arrays yielded mean absolute errors of 48–66 nm and coefficients of variation of 2.0–3.9%, confirming resolution and reproducibility across large areas. Importantly, OFETs based on patterned PBTTT exhibited charge-carrier mobility, threshold voltage, and on/off ratios comparable to spin-coated devices, despite undergoing multiple photolithography steps, indicating preservation of transport characteristics. Furthermore, the same DISC-assisted lithography was successfully applied to other representative p-type conjugated polymers, including P3HT and PDPP-4T, confirming the universality of the method. This scalable strategy thus combines the precision of established lithography with the functional advantages of organic semiconductors, providing a robust platform for high-density organic electronic integration in flexible circuits, biointerfaces, and active-matrix systems. Full article

The electrochemical capture and transformation of carbon dioxide (CO₂) (ECC) has recently emerged as a transformative alternative to conventional sorbent-based processes, enabling fully reversible operation under mild conditions and direct compatibility with renewable energy sources. This review focuses on redox-active metal–organic frameworks (MOFs) as electrosorbent materials for the electrochemical capture of CO₂. Rather than encompassing all electrochemical CO₂ capture technologies, we use molecular, polymeric, and COF-based systems as a framework to define what makes a MOF truly “redox-active” for CO₂ electrosorption and how its performance can be assessed. This includes capacitive versus faradic electrosorption mechanisms and design strategies based on the redox chemistry associated with metal nodes, π-conjugated ligands, and strongly redox-active units such as tetrathiafulvalene, viologen, and ferrocene. The way in which defects affect hybrid MOF composites was highlighted, and in situ and operando spectroscopic techniques have improved the understanding of the reaction mechanism in carbon dioxide capture and release under controlled potential. Research comparing carbonaceous materials, redox polymers, and hybrid structures has highlighted both the opportunities and limitations of MOFs, particularly in terms of energy efficiency, scalability, structural robustness, and reproducibility. From a broader perspective, redox-active MOFs occupy a unique position at the intersection of coordination chemistry, electrochemistry, and materials engineering for large-scale applications. In this review, we analyze how redox activity in MOFs—at the metal nodes, ligands, and extended structures—can be harnessed to design energy-efficient, cyclic electrochemical CO₂ capture systems. Furthermore, we propose cross-cutting metrics and design rules that enable meaningful comparisons between materials and device architecture. Full article

Porphyrins are conjugated tetrapyrrolic macrocycles with tunable photophysical and catalytic properties, while covalent organic frameworks (COFs) are crystalline, porous polymers built from robust covalent linkages. Combining these motifs yields porphyrin-based COFs that couple ordered porosity with light-harvesting and metal-anchoring capabilities, offering promise for carbon dioxide capture and conversion. This review provides an integrated overview of their design, synthesis, structure, and function in the context of CO₂ capture, storage, and photocatalytic/electrocatalytic reduction. We survey recent literature, organize materials by linkage chemistry and topology, and summarize metallation, peripheral functionalization, and heterostructure strategies, compiling representative performance metrics where reported. The collected studies indicate that appropriate metallation and π-extension enhance light absorption and charge separation; high crystallinity and accessible pores facilitate mass transport; and electronic coupling to conductive phases improves catalytic activity and selectivity in CO₂ reduction. We close by outlining challenges and opportunities, including improving charge transport without sacrificing stability, pinpointing and quantifying active sites, and operando characterization to connect structure with function. This objective synthesis is intended to guide rational design of porphyrin-COFs for efficient and durable CO₂ management. Full article

In alkaline water electrolysis, conventional polymer binders like Nafion suffer from poor hydroxide conductivity and inadequate interfacial properties. Herein, a thermally cyclized polyacrylonitrile (CPAN) binder system with a conjugated ladder structure is introduced. The CPAN binders are synthesized by controlled thermal treatment under various temperatures, among which CPAN-400 demonstrates the optimal 57.03% pyridinic N content, provides π-conjugated pathways for enhanced electronic conductivity, and indicates hierarchically porous electrode architectures. The NiFe/CPAN-400 electrode achieves enhanced oxygen evolution performance with an overpotential of 354 mV at 100 mA cm⁻², which is 153 mV and 103 mV lower than NiFe–Nafion and NiFe–PAN, respectively. This enhancement results from synergistic effects, including an electrochemically active surface area increased 2.3-fold, improved electrolyte wettability, and optimized charge transfer kinetics. The pyridinic nitrogen-enriched structure also facilitates a rate-determining step transition from charge transfer to *OOH formation, with a Tafel slope of 59.9 mV dec⁻¹. This work establishes thermally induced polymer cyclization as a versatile strategy for advanced binder developments. Full article

Thanks to their multiple outstanding features—such as high fluorescence quantum yield, good photostability, and excellent sensitivity—conjugated polymers (CPs) have emerged as a pioneering class of fluorescent materials for sensing applications, particularly in environmental and biological fields, for the detection of a wide range of environmental pollutants and bioactive compounds. The presence of delocalized π-electrons in the CP backbone significantly enhances sensing performance through a unique phenomenon known as the “molecular wire effect.” As a result, CP-based fluorescent sensors have been extensively developed and employed as exceptional tools for monitoring various analytes in environmental and biological contexts. A deep understanding of their unique properties, fabrication techniques, and recent innovations is essential for guiding the strategic development of advanced CP-based fluorescent sensors, particularly for future point-of-care applications. This study presents a critical review of the key characteristics of fluorescent sensors and highlights several common types of conjugated polymers (CPs) used in their design and fabrication. It summarizes and discusses the main sensing mechanisms, state-of-the-art applications, and recent innovations of CP-based fluorescent sensors for detecting target compounds in environmental and biological fields. Furthermore, potential strategies and future perspectives for designing and developing high-performance CP-based fluorescent sensors are emphasized. By consolidating current scientific evidence, this review aims to support the advancement of highly sensitive fluorescent sensors based on various CP nanoparticles for environmental and biological applications. Full article

Hybrid materials based on porous organic polymers (POPs) and metal–organic frameworks (MOFs) are increasing attention for advanced separation processes due to the possibility to combine their properties. POPs provide high surface areas, chemical stability, and tunable porosity, while MOFs contribute a high variety of defined crystalline structures and enhanced separation characteristics. The combination (or hybridization) with PIMs gives rise to mixed-matrix membranes (MMMs) with improved permeability, selectivity, and long-term stability. However, interfacial compatibility remains a key limitation, often addressed through polymer functionalization or controlled dispersion of the MOF phase. MOF/COF hybrids are more used as biochemical sensors with elevated sensitivity, catalytic applications, and wastewater remediation. They are also very well known in the gas sorption and separation field, due to their tunable porosity and high electrical conductivity, which also makes them feasible for energy storage applications. Last but not less important, hybrids with other POPs, such as hyper-crosslinked polymers (HCPs), covalent triazine frameworks (CTFs), or conjugated microporous polymers (CMPs), offer enhanced functionality. MOF/HCP hybrids combine ease of synthesis and chemical robustness with tunable porosity. MOF/CTF hybrids provide superior thermal and chemical stability under harsh conditions, while MOF/CMP hybrids introduce π-conjugation for enhanced conductivity and photocatalytic activity. These and other findings confirm the potential of MOF-POP hybrids as next-generation materials for gas separation and carbon capture applications. Full article

The strategic design of donor–acceptor (D-A) conjugated porous polymers has emerged as a pivotal methodology for advancing efficient photocatalytic hydrogen evolution. However, conventional D-A polymeric architectures face inherent limitations: excessively strong acceptor units may lower the LUMO energy level, compromising proton (H⁺) reduction capability, while weak D-A interactions result in inadequate light-harvesting capacity and insufficient photogenerated electrons, ultimately diminishing photocatalytic activity. To address these challenges, we developed a new D1-A-D2 conjugated porous polymer (CPP) system. The strategic incorporation of a secondary donor benzothiophene (DBBTh) unit enabled precise bandgap engineering in D₁-A-D₂ CPPs. Experimental results demonstrate that DBBTh integration significantly enhances both light absorption efficiency and proton reduction ability. Under visible-light irradiation (λ > 420 nm), the Py-BKh1 photocatalyst achieved a hydrogen evolution rate (HER) of 10.2 mmol h⁻¹ g⁻¹ with an apparent quantum yield (AQY) of 9.5% at 500 nm. This work provides a groundbreaking paradigm for designing high-performance organic photocatalysts. Full article

Water pollution is a critical environmental issue in modern society, and adsorption is recognized as a straightforward and efficient water purification technique. In this study, three new viologen-based ionic porous organic polymers were designed and successfully synthesized via a simple approach, and their adsorption properties for water pollutants were evaluated. The cationic nature of these polymers, coupled with their large conjugated π-electron system, physicochemical stability, and aromatic backbone, contributes to their high adsorption capacity and rapid adsorption efficiency for anionic contaminants in water such as Methyl Orange, Congo Red, and Cr (VI). The polymers exhibited maximum adsorption capacities of 1617 mg/g for MO, 3734 mg/g for CR, and 530.22 mg/g for Cr (VI), surpassing most previously reported adsorbents. Furthermore, the polymers maintained a high removal rate even in the presence of competing anions. Effective separation of anionic dyes from mixed solutions could be achieved through simple filtration. These characteristics make them promising candidates for water purification applications. Full article

As a key means to solve energy and environmental problems, photocatalytic technology has made remarkable progress in recent years. Organic semiconductor materials offer structural diversity and tunable energy levels and thus attracted great attention. Among them, porphyrin and its derivatives show great potential in photocatalytic reactions and light therapy due to their unique large-π conjugation structure, high apparent quantum efficiency, tailorable functionality, and excellent biocompatibility. Compared to unassembled porphyrin molecules, supramolecular porphyrin assemblies facilitate the solar light absorption and improve the charge transfer and thus exhibit enhanced photocatalytic performance. Herein, the research progress of porphyrin-based supramolecular assemblies, including the construction, the regulation of charge separation and transfer, stability, and application in photocatalysis, was systematically reviewed. The construction strategy of porphyrin supramolecules, the mechanism of charge separation, and the intrinsic relationship of assembling structure-charge transfer-photocatalytic performance received special attention. Surfactants, peptide molecules, polymers, and metal ions were introduced to improve the stability of the porphyrin assemblies. Donor-acceptor structure and co-catalysts were incorporated to inhibit the recombination of the photoinduced charges. These increase the understanding of the porphyrin supramolecules and provide ideas for the design of high-performance porphyrin-based photocatalysts. Full article

π-conjugated polymers are arguably one of the most exciting classes of materials and have attracted substantial attention due to their unique optical and electronic properties. The introduction of transition metals into conjugated polymers tunes the optoelectronic properties of these metallopolymers, which may improve their performance in device applications. Graphene and reduced graphene oxide (RGO) derivatives are interesting materials with a unique structure and outstanding properties. The present work reports an investigation of three hybrid RGO and π-conjugated oligomers that contain ruthenium polypyridyl chromophores serving as models to provide molecular-level insight for the corresponding transition-metal-containing conjugated polymers. Full article

Designing novel π-conjugated conductive polymers with abundant redox-active groups is a viable route to achieve high charge storage performance for aqueous energy storage devices. Electropolymerization is a powerful tool to construct conductive polymers. Here, s-triazine is, for the first time, electropolymerized in an aqueous acidic solution on carbon cloth. The polytriazine-coated carbon cloth electrode (PT/CC) exhibits a granular structure, with abundant pores. The charge storage performance is investigated, and a specific capacity of 101.4 mAh ${\mathrm{g}}^{-1}$ at 1 A ${\mathrm{g}}^{-1}$ in 1 M ${\mathrm{H}}_2{\mathrm{S}\mathrm{O}}_4$ is achieved. Additionally, in 1 M ZnSO₄, a specific capacity of 50.3 mAh ${\mathrm{g}}^{-1}$ at 1 A ${\mathrm{g}}^{-1}$ can be achieved by the PT/CC. The PT/CC behaves as a battery-type charge storage electrode, and the amino/imino and carbonyl/hydroxyl groups contribute to the charge storage, with cation insertion and extraction. A symmetric aqueous charge storage device assembled with two PT/CC electrodes exhibits an energy density of 12.92 Wh ${\mathrm{k}\mathrm{g}}^{-1}$ and a power density of 250 W ${\mathrm{k}\mathrm{g}}^{-1}$ at 1 A ${\mathrm{g}}^{-1}$. After 2500 cycles at 10 A ${\mathrm{g}}^{-1}$, the device retains a specific capacity of 83.3%. This study indicates that the PT is a potential candidate material for an aqueous energy storage device. Full article

The electrochromic phenomenon of conducting polymer is mainly dominated by the π-π* band transition. The π conjugation is influenced by the coplanarity between polymer units, deviations from which can lead to an increased ionization potential and band gap values. In order to investigate the effect of plane distortion angle on electrochromic color in the main chain structure of polymerization, high-performance poly(3,3′-dimethyl-2,2′-bithiophene) (PDMeBTh) with a large plane distortion angle is successfully synthesized in boron trifluoride diethyl etherate (BFEE) by the electrochemical anodic oxidation method. The electrochemical and thermal properties of PDMeBTh prepared from BFEE and ACN/TBATFB are compared. The electrochromic properties of PDMeBTh are systematically investigated. The PDMeBTh shows a different color change (orange-yellow in the neutral state) compared to poly (3-methylthiophene) (light-red in the neutral state) due to the large torsion angle between thiophene rings of the main polymer chain. The optical contrast, response time, and coloring efficiency (CE) of the prepared PDMeBTh are also studied, which shows good electrochromic properties. For practical applications, an electrochromic device is fabricated by the PDMeBTh and PEDOT. The color of the device can be reversibly changed between orange-yellow and dark blue. The light contrast of the device is 27% at 433 nm and 61% at 634 nm. The CE value of the device is 403 cm² C⁻¹ at 433 nm and 577 cm² C⁻¹ at 634 nm. The constructed device also has good open circuit memory and electrochromic stability, showing good potential for practical applications. Full article

Thin films of poly(arylene ethynylene)-conjugated polymers, including low-energy-gap donor–acceptor polymers, can be prepared via stepwise polymerization utilizing surface-confined Sonogashira cross-coupling. This robust and efficient polymerization protocol yields conjugated polymers with a precise molecular structure and with nanometer-level control of the organization and the uniform alignment of the macromolecular chains in the densely packed film. In addition to high stability and predictable and well-defined molecular organization and morphology, the surface-confined conjugated polymer chains experience significant interchain electronic interactions, resulting in dominating intermolecular π-electron delocalization which is primarily responsible for the electronic and spectroscopic properties of polymer films. The fluorescent films demonstrate remarkable performance in chemosensing applications, showing a turn-off fluorescent response on the sub-ppt (part per trillion) level of nitroaromatic explosives in water. This unique sensitivity is likely related to the enhanced exciton mobility in the uniformly aligned and structurally monodisperse polymer films. Full article

A novel approach towards synthesizing new metalloid-substituted olefins has been accomplished by transforming (E)-1,2-diboryl-1-silylethenes through two consecutive Suzuki–Miyaura coupling reactions. This methodology provides an effective and selective way to obtain new, structurally different products, such as (E)-1-silyl-1-boryl-2-arylethens, (1E,3E)-1-silyl-1-boryl-2-alkenylethens, and (E)-1-silyl-1-aryl₁-2-aryl₂ethenes, which are difficult to synthesize through hydrometallation reactions and related processes. Due to the presence of reactive motifs (silyl group, Bpin moiety, and C_sp2-H bond) in the structure of the final products, these molecules might be considered powerful building blocks in modern chemistry. With the aid of demetallation and cross-coupling reactions, they might be further functionalized into several invaluable chemicals, i.e., tetrasubstituted olefins (anti-cancer drugs, fluorescence materials), compounds with high π-conjugation, and polymers. Full article

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 (Φ_fl = 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. Full article