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This article explores the shift in chemical physics research towards studying single molecules and nanoparticles instead of bulk samples. Advancements in experimental techniques, such as single-molecule absorption and fluorescence spectroscopy, have made this shift possible. The article discusses various observations made through single-molecule spectroscopy, as well as theoretical considerations and applications in biology, materials science, and nanophotonics. It provides a summary of studies conducted using single-molecule spectroscopy in different disciplinary categories, demonstrating its interdisciplinary nature. The article concludes by discussing the challenges and future directions in the field, including integrating particle tracking with time-dependent spectroscopy and actively manipulating nanoscale objects. [Extracted from the article]

Polymer dielectrics with excellent capacitive performance are urgently needed in advanced electrical and electronic systems. However, due to the dramatic increase in the conduction loss, the energy density and efficiency of polymers degrade severely at elevated temperatures, limiting their application in harsh environments up to 150 °C. Herein, an all-organic polyurea (PU)/polyetherimide (PEI) blend film is designed to prepare high-temperature polymer dielectric. It is found that carrier traps can be introduced by blending, and the hydrogen bond between PU and PEI increases the trap depth, leading to suppressed leakage current and enhanced breakdown strength, thus improving the energy storage performance. PU/30%PEI exhibits a high discharged energy density of ∼3.74 J/cm3 with an efficiency higher than 90% at 150 °C, which is 78% and 70% higher than pristine PU and PEI, respectively. This work provides a facile strategy to improve the energy storage performance of polymer dielectrics by introducing deep traps through blending. [ABSTRACT FROM AUTHOR]

Organic photovoltaic devices (OPVs) are attracting attention because of recent rapid enhancement of their power conversion efficiency. For further improvement, optimization of fabrication processes is one useful path to a solution. During OPV fabrication, particularly of the bulk heterojunction active layer, annealing treatments contribute to the device performance. Many studies have examined annealing-related properties. However, further research must clarify how paramagnetic species in the devices play their roles by annealing. Using well-known OPVs, we investigated the relation between spin-dependent recombination (SDR) current and the paramagnetic species, which vary the numbers by post-annealing with active layers consisting of poly(3-hexylthiophene-2,5-diyl) (P3HT) and [6,6]-phenyl-C 61 -butyric acid methyl ester (PC 61 BM). A simultaneous detection method of electron spin resonance (ESR) and electrically detected magnetic resonance (EDMR), which we originally developed, was applied to OPVs for the first time ever reported. Results show that PC 61 BM anion radicals generated by post-annealing of P3HT:PC 61 BM OPVs with a lithium fluoride (LiF)/aluminum (Al) electrode do not contribute to the SDR current at the interface and that P3HT cation radicals enhance the SDR current. By contrast, devices with an Al electrode without LiF decrease the total SDR current, although the quantities of cation radical molecules do not vary. This finding suggests that changes of the hole blocking layer in the devices caused by the annealing treatment affect the size of capture cross sections of P3HT cation radicals. Our new method of quantitative observation of the EDMR changes through the ESR signals is expected to be useful for investigating the capture cross sections in OPVs. [ABSTRACT FROM AUTHOR]

π-conjugated polymers have been used in a wide range of practical applications, partly due to their unique properties that originate in the delocalization of electrons through the polymer backbone. The level of delocalization can be characterized by the induced bond length alternation (BLA), with shorter BLA connected with strong delocalization and vice versa. The accurate description of this structural parameter can be considered a benchmark for testing the capability of different electronic structure methods for self-interaction error (SIE) removal and electron correlation inclusion. Density functional theory (DFT), in its local or semi-local flavors, suffers from SIE and, thus, underestimates the BLA compared to self-interaction-free methods. In this work, we utilize the Fermi–Löwdin orbital self-interaction correction (FLOSIC) method for one-electron self-interaction removal to characterize the BLA of five oligomers with increasing length extrapolated to the polymeric limit. We compare the self-interaction-free BLA to several DFT approximations, Møller–Plesset second-order perturbation theory (MP2), and the BLA obtained with the domain based local pair natural orbital CCSD(T) [DLPNO-CCSD(T)] approximation. Our findings show that FLOSIC corrects for the small BLA given by (semi-)local DFT approximations, but it tends to overcorrect with respect to CAM-B3LYP, MP2, and DLPNO-CCSD(T). [ABSTRACT FROM AUTHOR]

Understanding and modulating the spin-pair correlation of conjugated polymer materials in π-conjugated polymer light-emitting devices (PLEDs) plays a crucial role in the development of their applications. We investigated the relationships between the internal hyperfine interactions (HFIs), triplet–triplet annihilation (TTA), and triplet–charge annihilation (TCA) spin evolution processes in π-conjugated PLED. Research has shown that in a unipolar π-conjugated PLED, the "M" shaped ultra-small magnetic field effect is due to the HFI between hole polarons and the spin-mixing process of charge carriers. Under high magnetic fields (15 mT<|B|<350 mT), the TCA process dominates the negative magneto-conductance (MC), and its intensity and sign are not controlled by temperature. In polar π-conjugated PLED, excess carriers can provide conditions for the generation of TCA. Moreover, π-conjugated polymers (emission layers) have relatively strong electron–phonon coupling, which can capture triplet excitons into adjacent organic layers to obtain higher triplet exciton concentrations, resulting in the TTA process. Under low-temperature conditions, excess carriers induce the magneto-electroluminescence (MEL) effect to undergo TTA and form P-type delayed fluorescence. This study can provide a new mechanism explanation for the HFI in PLED devices and a new approach for the effective utilization of triplets. [ABSTRACT FROM AUTHOR]

The type of aggregation in conjugated polymers determines their use in electronic devices. H-type aggregates are most suitable for solar cell applications, while J-type aggregates are recommended for light-emitting diodes. In this work, we used three methods to determine the type of aggregates in a benzodithiophene–isoindigo-based (PBDTI-DT) copolymer, namely, Huang–Rhys factor evolution with temperature, Franck–Condon analysis, and relative quantum yield (QY) calculation. All three methods indicate that both aggregation types are present, and the QY calculation clearly indicates that H-aggregates are more dominant. Time-dependent density functional theory was used to identify the two absorption bands of PBDTI-DT as local π − π* and intramolecular charge-transfer transitions. [ABSTRACT FROM AUTHOR]

The New Journal of Chemistry, published by The Royal Society of Chemistry and the Centre National de la Recherche Scientifique, is a scientific journal that aims to connect the world with the chemical sciences. The contents list for the September 21, 2024 issue includes a variety of articles and papers on topics such as the synthesis of nanomaterials, nonlinear optical crystals, and the detection of formaldehyde. The journal provides recognition and professional development opportunities for scientists. Some specific papers in this issue cover the preparation of superhydrophobic/superhydrophilic sodium alginate aerogels for oil absorption, improved efficiency of quantum dot-sensitized solar cells, and the electrocatalytic activity of nickel-doped manganese oxide nanorods. Other topics include the synthesis of nanocomposites for supercapacitor performance, the selective adsorption and photodegradation of residual norfloxacin in water, and the targeted delivery of ifosfamide for cancer treatment. [Extracted from the article]

In this study, we present a pioneering approach for the electrochemical detection of levofloxacin (LVO) in human blood serum utilising iron vanadate nano-bulbs FeVO4 (FVO) decorated on a two-dimensional conjugated polymer matrix g-C3N4 (CN). The iron vanadate nano-bulbs are synthesised via a simple hydrothermal approach and integrated into a 2D conjugated polymer matrix, providing a high surface area and numerous active sites for improved sensing of LVO with a detection limit of 0.06 μM, a broader linear range of 0.25–320 μM, and high sensitivity and selectivity towards LVO. The findings highlight the significant role of vanadium in electrocatalysis, unveiling the sensor's enhanced electrochemical properties and repeatability, reproducibility and stability. This work underscores the potential of FVO nano-bulbs in developing efficient and sensitive electrochemical sensors for pharmaceutical monitoring, providing a valuable tool for real-time drug toxicity analysis. [ABSTRACT FROM AUTHOR]

Stretchable organic photovoltaics (OPVs) are pivotal for advancing conformable electronics, yet achieving both efficient and intrinsically stretchable OPVs remains a significant challenge. The main issue is maintaining electronic and mechanical properties under deformation. Here, a ternary blend system, PTzBI‐oF:PYIT:EVA is presented, incorporating ethylene‐vinyl acetate (EVA) to establish a conjugated and elastomeric dual‐network morphology. The elastomer network dissipates applied stress, preserving the crystalline packing of the conjugated network and enabling improved mechanical stability of charge carrier generation and transport. Specifically, with 15% EVA content, the ternary blend achieved a power conversion efficiency (PCE) of 15.28% in rigid devices and exhibited a crack onset strain of 17.23%. Notably, the stretchable OPVs retained over 80% of their initial PCE under 30% strain. These findings underscore the potential of conjugated and elastomeric dual‐network morphology in developing high‐performance stretchable electronics for various applications. [ABSTRACT FROM AUTHOR]

[Display omitted] The diversity of catalytic products determines the difficulty of selective product modulation, which usually relies on adjusting the catalyst and reaction conditions to obtain different main products selectively. Herein, we synthesized D-π-A-D conjugated organic polymers (TH-COP) using cyclotriphosphonitrile, alkyne, 2H-benzimidazole, and sulfur units as electron donors, π bridges, electron acceptors, and electron donors, respectively. TH-COP exhibited excellent photoinduced carrier separation and redox ability under different visible light wavelengths, and the main products of its CO 2 reduction are CH 4 (1000.0 μmol g−1) and CO (837.0 μmol g−1) under 400–420 nm and 420–560 nm, respectively. In addition, TH-COP could completely convert phenylmethyl sulfide to methyl phenyl sulfone at 400–420 nm and diphenyl disulfide at 480–485 nm in yields up to 95 %. This study presents a novel strategy for the targeted fabrication of various main products using conjugated polymers by simply changing the wavelength range of visible light. [ABSTRACT FROM AUTHOR]

Pathogenic bacteria are closely associated with the occurrence, development and metastasis of oral squamous cell carcinoma (OSCC). Antibacterial therapy has been considered an enhancement strategy to suppress bacteria-associated tumors and promote anti-tumor immune responses. Herein, we developed an injectable adhesive hydrogel, PNIPAM/DL@TIR, for the in situ photothermal ablation and robust stimulation of antitumor immunity against OSCC colonized by Porphyromonas gingivalis (Pg), one of the major oral pathogenic bacteria. PNIPAM/DL@TIR, composed of poly(N-isopropylacrylamide), demethylated lignin, and TAT peptide-conjugated IR820, was prepared using a simple dissolve-dry-swell solvent exchange method. Upon 808 nm laser irradiation, PNIPAM/DL@TIR exerted photothermal effects to ablate Pg-colonized OSCC and generate dual tumor and bacterial antigens. Owing to its large number of catechol groups, PNIPAM/DL@TIR efficiently captured these antigens to form an in situ antigen repository, thereby eliciting robust and durable antitumor immune responses. Proteomic analysis revealed that the captured antigens comprised both tumor neoantigens and bacterial antigens. The catechol groups endowed PNIPAM/DL@TIR with antioxidant activity, which was also conducive to stimulating antitumor immunity. Altogether, this study develops an injectable adhesive hydrogel and provides a combination strategy for treating bacteria-associated OSCC. In this study, we developed an injectable adhesive hydrogel, PNIPAM/DL@TIR, for in situ photothermal ablation and robust stimulation of antitumor immunity against OSCC colonized by Porphyromonas gingivalis , one of the major oral pathogenic bacteria. PNIPAM/DL@TIR, which consists of poly(N-isopropylacrylamide), demethylated lignin, and TAT peptide-conjugated IR820 exhibited outstanding photothermal performance. Owing to the presence of catechol groups, PNIPAM/DL@TIR has good bioadhesive properties and can capture protein antigens to form in situ antigen repository, thus initiating robust and long-term antitumor immune responses. In addition, PNIPAM/DL@TIR exhibited strong antioxidant activity that is favorable for promoting antitumor immunity. In the mouse model of OSCC with bacterial infection, PNIPAM/DL@TIR not only ablated the primary tumors upon NIR laser irradiation, but also induced tumor and bacterial vaccination in situ to suppress distant tumors and lung metastasis. [Display omitted] [ABSTRACT FROM AUTHOR]

The nature of interchain π-system contacts, and their relationship to hole transport, are elucidated for the high-mobility, noncrystalline conjugated polymer C16-IDTBT by the application of scanning tunneling microscopy, molecular dynamics, and quantum chemical calculations. The microstructure is shown to favor an unusual packing motif in which paired chains cross-over one another at near-perpendicular angles. By linking to mesoscale microstructural features, revealed by coarse-grained molecular dynamics and previous studies, and performing simulations of charge transport, it is demonstrated that the high mobility of C16-IDTBT can be explained by the promotion of a highly interconnected transport network, stemming from the adoption of perpendicular contacts at the nanoscale, in combination with fast intrachain transport. [ABSTRACT FROM AUTHOR]

AbstractNanodiamonds have been researched as sphere-shaped carbon nano-entities having countless surface/structural properties, facile fabrication and mammoth technological value. An important utilization of nanodiamonds has been observed as nano-reinforcing agents for nanocompositing purposes. Semiconducting polymers (conjugated polymers) having π electron delocalization have been documented for worthy electrochemical/optical/thermal/mechanical features, in addition to the electron transfer through their backbone. Doping of carbonaceous nanoparticles, like nanodiamonds, with conjugated polymers have been found to further improve the valuable physical characteristics in their final nanocomposite form. Correspondingly, this overview describes the impact of nanodiamond nano-reinforcement on the specialized aspects of polyaniline/nanodiamond, polypyrrole/nanodiamond and polythiophene/nanodiamond nanocomposites. According to literature reports, these groupings of conjugated polymer/nanodiamond hybrids revealed noteworthy microstructural, conductive, optical, electrochemical, microwave absorption, specific capacitance, photovoltaic and actuation characteristics. Subsequently, several significant applications of polymer/nanodiamond nanomaterials have been explored including the solar cells, supercapacitors and actuators. [ABSTRACT FROM AUTHOR]

We report a bioinspired approach to tune surface nanostructures by soft‐template electropolymerization in micellar conditions. Monomers highly favoring π‐stacking interactions are particularly interesting for favoring the polymer deposition in one direction. Here, original triphenylamine‐based monomers di‐substituted by thiophene and carbazole are investigated. Conjugated building blocks monomers are tested to favor deposition vs polymerization, even if the monomers are not perfectly planar. The carbazole derivatives have a much higher electrodeposition capacity than the thiophene derivatives, which is unexpected if thiophene and carbazole are taken alone. Moreover, in all electrodeposited films, monomer seems to be present as shown by cyclic voltammetry experiments, confirming previous works. The amount of monomer vs oligomers is highly dependent on the investigated monomer. For the resulting surface structures, hollow spheres and nanoribbons are particularly formed with some investigated monomers by cyclic voltammetry while nanotubes are observed at constant potential. The formation of nanotubes indicates a polymer growth more favored in one direction. These surfaces are less hydrophobic (water contact angle up to 111.5°) compared to films with spherical nanoparticles but these results can be explained only by the presence of air inside the surface roughness. [ABSTRACT FROM AUTHOR]

Heterocyclic organic semiconductors have attracted significant attention as photocatalysts for hydrogen evolution due to excellent absorbency and abundant active sites. Herein, we developed a dual heterocyclic (O/S) conjugated microporous polymer Py-Th-Fu, consisting of both the furan and thiophene heterocycles, for photocatalytic H 2 evolution. Compared with the furan O-heterocycle Py-Fu and thiophene S-heterocycle Py-Th, the Py-Th-Fu with the dual heterocyclic structure is more outstanding in regulating the optoelectronic properties, morphological properties, electric charge shift kinetics, and photocatalytic H 2 evolution activity. Computational analysis also elucidates the smallest hydrogen adsorption free energy of Py-Th-Fu, which suggests it is the most advantageous for hydrogen mass transfer in this dual heterocycle polymer. As a result, the synergistic combination of two different heteroatom catalytic sites enables the dual heterocycle Py-Th-Fu to afford enhanced catalytic activity with an optimal rate of 23.28 mmol g−1 h−1, which is nearly equal to 5.06 and 1.58 times that of the corresponding O- and S-containing single heterocycles Py-Fu and Py-Th under visible lighting (λ > 420 nm). Our study demonstrates that the dual heterocyclic strategy using ternary copolymerization to tune the optoelectronic properties may open the horizon for fabricating high-performance photocatalytic water splitting via sunlight-driven hydrogen evolution. [Display omitted] • We developed a CMP photocatalyst with double heterocyclic strategy. • This strategy regulated the morphological properties and charge transfer kinetics. • Double heterocycle exhibited better HER than the single heterocycle in CMPs. [ABSTRACT FROM AUTHOR]

Fully π-conjugated polymers with rigid aromatic units are promising for flexible optoelectronic devices, but their inherent brittleness poses a challenge for achieving high-performance, intrinsically stretchable fully π-conjugated polymer. Here, we are establishing an external-plasticizing strategy using semiconductor fluid plasticizers (Z1 and Z2) to enhance the optoelectronic, morphological, and stretchable properties of fully π-conjugated polymer films for flexible light-emitting diodes. The synergistic effect of hierarchical structure and optoelectronic properties of Z1 in poly(9,9-di-n-octylfluorene-alt-benzothiadiazole) (F8BT) films enable excellent stretchable deformability (~25%) and good conductivity. PLEDs based on F8BT/Z1 films show stable electroluminescence and efficiency under 15% stretch and 100 cycles at 10% strain, revealing outstanding stress tolerance. This strategy is also improving the stretchable properties of polymers like poly(9,9-di-n-octylfluorenyl-2,7-diyl) (PFO) and poly(2-methoxy-5(2′-ethyl)hexoxy-phenylenevinylene) (Super Yellow), demonstrating its general applicability. Therefore, this strategy can provide effective guidance for designing high-performance stretchable fully π-conjugated polymers films for flexible electronic devices. The realization of intrinsically stretchable fully π-conjugated polymer film is challenging due to their inherent brittle nature. Here, authors apply semiconductor fluid molecular plasticizers to improve stretchable deformability, achieving high performance flexible polymer light-emitting diodes. [ABSTRACT FROM AUTHOR]

The significant interfacial resistance between solid electrolyte‐electrode interfaces is a major bottleneck for the practical application of solid‐state lithium batteries. This resistance is primarily caused by the formation of space charge layers (SCLs), resulting from the redistribution of ionic carriers at the interface between dissimilar materials with varying chemical potentials, which lead to insufficient carriers and sluggish lithium‐ion transport. In this study, a conjugated structure polymer is constructed through in situ polymerization onto the oxide electrolyte, forming charge‐rich SCLs on the organic/inorganic interface, and enabling the interfacial layer to maintain superior ion transfer and contact. The Li solid NMR spectra and computational study suggest that optimized SCLs offer effective pathways for Li+ conduction in the electrolyte, thereby enhancing the interfacial conduction. Furthermore, the designed electrolyte induces the formation of an inorganic‐rich interphase layer on the lithium anode, enabling rapid lithium‐ion transport and uniform Li deposition. Consequently, the lithium symmetric cell with this electrolyte operates for more than 5100 h, while LiFePO4/Li solid‐state batteries can stably cycle up to 800 times at 5 C. This interfacial modification strategy provides a new perspective for the rational design of the charge‐rich SCLs and advances the understanding of the SCLs inside the electrolyte. [ABSTRACT FROM AUTHOR]

Low efficiency of photogenerated electron–hole separation has been a challenge for organic conjugated polymer photocatalysts. Our preceding studies have revealed that polymers containing B←N coordination bonds can form a localized built-in electric field that effectively promotes photogenerated charge separation. However, B←N coordination units are still scarce and require more examples to find regularities in their structural design. The systematic development and testing of B←N coordination units is necessary for the efficient development of subsequent polymers containing B←N coordination bonds. In this work, three conjugated polymers containing B←N coordination bonds, PBN–Ni, PBP–Ni, and PBS–Ni, were synthesized by changing the substituents of the boron atoms and introducing narrow-band thiophene units to form conjugate and energy band gradients. The energy band modulation and localized built-in electric field construction were both achieved as planned, while the bandgap and photogenerated charge transport capabilities caused performance discrepancies. The experimental results showed that PBN–Ni had a better photocatalytic hydrogen evolution (HER) performance, reaching 104.6 μmol h−1 (λ > 420 nm). The optimal optical absorption edge of PBS–Ni was up to 643 nm, but the HER was lower, at 33.2 μmol h−1 (λ > 420 nm, 1% Pt). PBP–Ni optimized some of the optical absorption efficiencies (511 nm) while ensuring the HER activity (96.6 μmol h−1, λ > 420 nm). This work tentatively explores the characterization of the B←N coordination bond-containing base units serving as photocatalysts and provides the basic model experience and data reference for the subsequent expansion of B←N coordination bond-containing units and the development of B←N coordination bond-containing copolymer systems. [ABSTRACT FROM AUTHOR]

We present a novel synthetic route for the rapid construction of dithieno[3′,2′:3,4;2′′,3′′:5,6]benzo[1,2‐c][1,2,5]thiadiazoles via Na2S‐promoted thiophene annulation. This method facilitated the synthesis of D18−Cl polymer, known for its efficacy as a polymer donor in bulk‐heterojunction polymer solar cells. Starting from commercially available 4,7‐dihalo‐5,6‐difluorobenzo[c][1,2,5]thiadiazole, various 4,7‐dialkynylated compounds were obtained through Sonogashira reaction conditions. Subsequent Na2S‐promoted thiophene annulations yielded DTBT and its derivatives in excellent yields within 10 minutes. DTBT was then utilized as a precursor for the concise synthesis of D18−Cl, benefiting from reduced synthetic steps, mild reaction conditions, decreased complexity, and high overall yields. In another route, a space group‐bridged DTBT was directly constructed via Na2S‐promoted thiophene annulations and converted into D18−Cl through a couple of steps. This developed protocol offers a straightforward and reliable synthetic tool, conducive to reducing complexities in the production of DTBT‐based organic electronic materials, thereby advancing the potential commercialization of organic solar cells. [ABSTRACT FROM AUTHOR]

This account summarizes the impact that the quest for sustainability is having on the field of organic polyconjugate molecules and polymers for plastic (opto)electronics. While at the proof-of-concept level, the design criteria as well as the preferred synthetic strategies to access new and improved materials have been dominated by the need for performance. The ongoing transition from the lab environment to the industrial scale imposes strict limitations on the cost and overall environmental impact of new materials. We here summarize our efforts on the development of new design criteria and synthetic strategies aimed at improving sustainability – without compromising performance – in organic polyconjugated molecules. The article is composed of three sections: Introduction and motivation, sustainability through improved synthetic methods and through improved design. Outline 1 Introduction and Motivation 2 Sustainable Reaction Methods 2.1 The New Tools: Reactions in Aqueous Solution of Surfactants 2.2 Intrinsically More Sustainable Reactions: Direct Arylation 2.3 Sustainable Multistep Protocols: Combining Micellar, Solventless, and Mechanochemical Methods 3 Sustainability as a Design Criterion: De Novo Design 4 Conclusion [ABSTRACT FROM AUTHOR]

Photocatalytic hydrogen evolution has attracted tremendous interest as it offers a process for generation of green hydrogen based on solar radiation. But the process is extremely complex as many factors influence photocatalytic hydrogen evolution. While novel photocatalysts such as MOFs, perovskites, conjugated polymers, carbon-based materials, quantum dots, and others face challenges such as stability and scalability, semiconductor photocatalysts and cocatalysts such as TiO 2 /Pt, Ni–CdS, CdS/ZnO, CdS/ZnS have the advantages of simplicity in synthesis, stability, and scalability. Despite decades of research, challenges such as charge separation, spectrum usage, low hydrogen generation efficiency, photocatalyst stability and scalability persist. This review discusses what has been achieved so far in the domain of photocatalytic hydrogen evolution and presents a critical analysis of challenges to be addressed in developing a robust and practical photocatalytic hydrogen generation system based on efficiency of photocatalysts and their stability and the extreme importance of efficient reactor designs. [Display omitted] • Challenges associated with photocatalytic hydrogen generation systems. • Photocatalysts, cocatalysts and their stability challenges in hydrogen evolution. • Potential of semiconductor nanostructures, plasmonic nanoparticles and QDs. • Importance of reactor designs in enhancing photocatalytic hydrogen evolution. [ABSTRACT FROM AUTHOR]

A viable tactic to effectively address the climate crisis is the production of renewable fuels via photocatalytic reactions using solar energy and available resources like carbon dioxide (CO2) and water. Organic polymer material-based photocatalytic materials are thought to be one way to convert solar energy into valuable chemicals and other solar fuels. The use of porous organic polymers (POPs) for CO2 fixation and capture and sequestration to produce beneficial compounds to reduce global warming is still receiving a lot of interest. Visible light-responsive organic photopolymers that are functionally designed and include a large number of heteroatoms and an extended π-conjugation allow for the generation of photogenerated charge carriers, improved absorption of visible light, increased charge separation, and decreased charge recombination during photocatalysis. Due to their rigid structure, high surface area, flexible pore size, permanent porosity, and adaptability of the backbone for the intended purpose, POPs have drawn more and more attention. These qualities have been shown to be highly advantageous for numerous sustainable applications. POPs may be broadly categorized as crystalline or amorphous according to how much long-range order they possess. In terms of performance, conducting POPs outperform inorganic semiconductors and typical organic dyes. They are light-harvesting materials with remarkable optical characteristics, photostability, cheap cost, and low cytotoxicity. Through cocatalyst loading and morphological tweaking, this review presents optimization options for POPs preparation techniques. We provide an analysis of the ways in which the preparative techniques will affect the materials' physicochemical characteristics and, consequently, their catalytic activity. An inventory of experimental methods is provided for characterizing POPs' optical, morphological, electrochemical, and catalytic characteristics. The focus of this review is to thoroughly investigate the photochemistry of these polymeric organic photocatalysts with an emphasis on understanding the processes of internal charge generation and transport within POPs. The review covers several types of amorphous POP materials, including those based on conjugated microporous polymers (CMPs), inherent microporosity polymers, hyper-crosslinked polymers, and porous aromatic frameworks. Additionally, common synthetic approaches for these materials are briefly discussed. [ABSTRACT FROM AUTHOR]

Polyelectrolytes are charged polymers comprising macromolecules in which substantial portions of the constituent units contain cationic (e.g., pyridinium, ammonium) or anionic (e.g., sulfonate, carboxylate) groups, which possess special functions from the features of counterions, such as dissociation to charged species, mechanical stability, phase behavior, etc. Therefore, functional polyelectrolytes have been widely applied in many fields. In this perspective, we present some progresses in the studies of poly(polyoxometalate)s, denoted as poly(POM)s, as a kind of new charged polymers/polyelectrolytes, by covalent bonding between the inorganic polyoxometalate (POM) clusters and the organic polymer chains. According to the distinct positions of POMs in polymer chain and functions of poly(POM)s, they are divided into the following four categories: crosslinked poly(POM); side-chain poly(POM); backbone poly(POM), including poly(POM)-conjugated polymer hybrid and block poly(POM)-polymer; and POM-based covalent organic framework (PCOF). This perspective introduces the synthesis methods of poly(POM) polyelectrolytes and their macromolecular and aggregate structural characteristics, while also focusing on their properties and functions. Their application areas include catalysis, thermal resistance, optical functions, fuel cells and batteries, etc. [ABSTRACT FROM AUTHOR]

Conjugated polymers (CPs) are widely used as conductive materials in various applications, with their conductive properties adjustable through chemical doping. While doping enhances the thermoelectric properties of CPs due to improved main-chain transport, overdoping can distort the polymer structure, increasing energy disorder and impeding intrinsic electrical transport. This study explored how different dopants affect the structural integrity and electrical transport properties of CPs. We found that dopants vary in their impact on CP structure, consequently altering their electrical transport capabilities. Specifically, ferric chloride (FeCl3)-doped indacenodithiophene-co-benzothiadiazole (IDTBT) shows superior electrical transport properties to triethyloxonium hexachloroantimonate (OA)-doped IDTBT due to enhanced backbone planarity and rigidity, which facilitate carrier transport and lower energetic disorder. These results highlight the critical role of dopant selection in optimizing CPs for advanced applications, suggesting that strategic dopant choices can significantly refine the charge transport characteristics of CPs, paving the way for their industrialization. [ABSTRACT FROM AUTHOR]

How plasmonic nanostructures modulate the behavior of exciplexes and excimers within materials remains unclear. Thus, advanced knowledge is essential to bridge this gap for the development of optoelectronic devices that leverage the interplay between plasmonic and conjugated polymer hybrid materials. Herein, this work aims to explore the role of gold nanoparticles (AuNPs) in modulating exciplex and excimer states within the conjugated polymer poly(2,5-di(3,7-dimethyloctyloxy) cyanoterephthalylidene) (PDDCP), known for its photoluminescent and semi-conductive properties, aiming to create innovative composite materials with tailored optical features. The spectral analysis was conducted to investigate the effects of AuNPs on the PDDCP, varying AuNP volume percentages to measure changes in the absorption profile, molar extinction coefficient (ε), absorption cross-section (σa), and optical bandgap ( E g ). Fluorescence spectra of the mixture at different volume ratios were also examined to assess exciplex formation, while amplified spontaneous emission (ASE) profiles were analyzed to study the behavior and photochemical stability of the polymer–NP hybrid material. Increasing AuNP volume induced both blue and red shifts in the absorption profile of the PDDCP. Higher AuNPs concentrations correlated with decreased ε and σa, inversely impacting E g . The emission spectra obtained at varied AuNP volume ratios indicated significantly enhanced exciplex and excimer formations. The ASE profiles remained consistent but showed reduced intensity with increasing AuNPs concentrations, indicating their influence on hybrid material behavior and stability. The findings suggest that AuNPs affect PDDCP's optical characteristics, altering the absorption profile, bandgap, and fluorescence spectra. Furthermore, the observed reduction in ASE intensity highlights their influence on the behavior and photochemical stability of the hybrid material. These results contribute to a better understanding of the versatile applications of plasmonic-conjugated hybrid polymers. [ABSTRACT FROM AUTHOR]

Organic conjugated polymers have received extensive attention due to their unique electronic properties. However, there have been relatively few reports on the dark photocatalytic reactions utilizing organic conjugated polymers. Herein, we report the successful synthesis of an organic conjugated polymer based on poly (heptazine imide) nanocrystals (CNNCs) for H2O2 evolution and biomedical applications using a simple salt molten method and sonication–centrifugation process. The results show that these colloid CNNCs have the characteristics of photogenerated electrons accumulation and realize dark photocatalysis with high reducibility under visible light irradiation. Notably, these accumulating photogenerated electrons can reduce O2 in darkness to produce H2O2. In addition, cytotoxicity tests were conducted and it was found that H2O2 produced under dark conditions could oxidize L-arginine (L-Arg) to NO, which effectively killed tumors in the dark. This work provides an important strategy to construct organic conjugated semiconductor nanocrystals and applying them to future energy and biomedical fields. [ABSTRACT FROM AUTHOR]

Temperature-responsive drug delivery systems offer the chance to better deliver anti-tumor drugs to tumor cells in a more controllable condition. In this work, a novel temperature-responsive nanocarrier was synthesized by grafting allyl alcohol and N-isopropyl acrylamide onto a nanodiamond surface and conjugated with polyester dendrimer for the controlled delivery of paclitaxel and photo-thermal therapy under near-infrared light irradiation. The morphology, chemical structure, and properties of this polymer were characterized through systematic characterization analyses. The data obtained from the non-linear isotherm model indicated that the sorption procedure followed Langmuir isotherm. Adsorption kinetic data shown that the pseudo-second-order model fitted well with the experimental results. The in-vitro drug release shown that about 92.10% of paclitaxel release was found to be occurred at the simulated physiological fluid within 48 h (pH 7.4; T = 45 °C), whereas about 64.38% of paclitaxel release occurred at the temperature of 37 °C (pH 7.4). Also, the released drug under near-infrared light irradiation reached up to 97.34% over 15 min, achieving the on-demand paclitaxel release. The release of the drug from the nanocarrier followed the mechanism of non-Fickian diffusion and best fitted to the Korsmeyer–Peppas model. The nanocarrier indicated dose dependent cytotoxicity towards MCF-7 cancer cells. [ABSTRACT FROM AUTHOR]

π‐Conjugated polyfluorenes (PPs) comprising 2,3‐diaminobenzene‐1,4‐diyl (unit A) and 9,9‐dihexylfluorene‐2,7‐diyl (polymer‐1) or 9,9‐bis(6‐N,N,N,‐trimethylammoniumhexyl)fluorene‐2,7‐diyl (unit B) (polymer‐2) units were synthesized using Suzuki‐Miyaura coupling polycondensation. To compare the chemical properties and functionality of polymer‐2, a water‐soluble PP comprising benzene‐1,4‐diyl and unit B (polymer‐3) was synthesized. Polymer‐1 exhibited solvatochromism: the photoluminescence (PL) peak of the polymer in solutions shifted to a longer wavelength with an increase in the dielectric constants of solvents. Polymer‐1 formed charge transfer (CT) complexes with organic electron acceptors. The CT complexation behavior was systematically elucidated by the PL measurements using Stern–Volmer and Benesi–Hildebrand methods. Water‐soluble polymer‐2 could be used as a sensor for the chain length of telomere DNA by monitoring the changes in its PL intensity upon the addition of the analyte. The DNA sensing performance of polymer‐2 surpassed that of polymer‐3, attributed to the presence of unit A in polymer‐2. This unit brought polymer‐2 closer to DNA through hydrogen bonding between the amino group of polymer‐2 and nucleic acids in DNA. This interaction facilitated the occurrence of CT from the polymer backbone to DNA. [ABSTRACT FROM AUTHOR]

Organic electrochemical transistors (OECTs) possess low operating voltage and excellent amplification capability and show promising applications in biosensors and flexible electronics. However, the active layers of OECTs are usually dense films, which show limited ion penetration/transport, resulting in limited performances of OECTs. Here, unprecedented high‐performance flexible multifunctional OECTs based on nanoporous (mainly 2–60 nm), high‐specific‐surface‐area (255–281 m2 g−1), and flexible conjugated polymer aerogel films are developed. The nanoporous structures effectively facilitate ion penetration/transport, leading to significantly enhanced transconductance (48.5–53.5 mS) and on/off ratio (6.4 × 104) of the OECTs compared with those of dense devices. The resulting OECT‐based glucose sensors exhibit an ultralow detection limit of 1 pm, approximately two to three orders of magnitude lower than those of the previously reported OECT glucose sensors, and an ultrabroad detection range of 1 pm–5 m. They can detect trace amounts of glucose in sweat, serum, saliva, and urine in real time. Moreover, the OECTs can be used for high‐performance flexible artificial synapses and electrocardiogram monitoring. This work provides a powerful strategy toward highly sensitive biosensors, artificial synapses, and electrophysiological signal monitoring. [ABSTRACT FROM AUTHOR]

The development of conjugated polymer–based water‐soluble nanoparticles for near‐infrared‐II (NIR‐II) fluorescence (FL; 1000–1700 nm)‐guided photothermal therapy holds promise in advancing cancer treatment. However, excessive nonradiative decay leads to almost complete quenching of conjugated polymers’ fluorescence. Therefore, a critical challenge is to suppress nonradiative decay while maintaining high‐quality fluorescence imaging and excellent photothermal conversion efficiency. In this study, a series of NIR‐II‐conjugated polymers with aggregation‐induced emission (AIE) effects are designed and synthesized using the Stille coupling reaction. The dual enhancement strategy of modulating the AIE units and introducing non‐conjugated backbone into the polymer backbone resulted in BCT1 with a high αAIE value of 3.27. BCT1 nanoparticles exhibit excellent NIR‐II fluorescence, a high photothermal conversion efficiency of 70.51%, and a tenfold enhancement in fluorescence compared with BT1. Both in vitro and in vivo experiments validated their good biocompatibility and outstanding performance in NIR‐II fluorescence imaging for accurately determining the location of tumors. This study provides a novel strategy and method for designing and developing multifunctional conjugated polymers for NIR‐II fluorescence imaging–guided photothermal therapy. [ABSTRACT FROM AUTHOR]

Polythiophenes are the most appealing donor materials in organic solar cells (OSCs) due to their simple chemical structures. However, the top‐performance polythiophenes are typically synthesized via Stille polycondensation, which is problematic due to significant toxicity and poor atom economy. By contrast, direct arylation polycondensation (DArP) is an eco‐friendly, and atom‐efficient alternative for synthesizing conjugated polymers, while the best efficiency for DArP‐derived polythiophenes is below 12%. This study reports a series of polythiophene‐based donors synthesized via DArP. Among these, PT4F‐Th reaches a power conversion efficiency (PCE) of 16.4%, which not only matches the current record for polythiophene‐based donor materials, but also marks the highest PCE achieved by DArP‐derived donors to date. The superior performance of PT4F‐Th is largely attributed to its optimal temperature‐dependent aggregation behavior and moderate miscibility with acceptors, along with the highest crystallinity among the candidates, resulting in the most favorable blend film morphology. This study underscores the significant potential of DArP‐derived polythiophenes in developing high‐performance and eco‐friendly OSCs. [ABSTRACT FROM AUTHOR]

Dibenzothiophene-S,S-dioxide (BTDO) is one of the cutting-edge electron-acceptor monomers for designing conjugated polymer based organic materials toward photocatalytic H 2 production from water. Normally, structure design of BTDO containing donor-acceptor (D-A) polymer photocatalyst mainly focuses on screening electron-donor motifs, the importance of modification on BTDO molecular toward improving charge carrier separation and photocatalytic performance is always ignored. Herein, a novel thienyl-fused BTDO building block (BTDO-DT) is prepared and utilized to synthesize B-BTDO-DT polymer photocatalyst by Sonogashira-Hagihara cross-coupling polycondensation using 1,4-Diethynylbenzene (B) and BTDO-DT as monomers. Experimental and density functional theory (DFT) calculation results demonstrate that modification of BTDO by thiophene not only enlarges light absorption region and promotes photogenerated e−/h+ separation, but also decreases H atom adsorption free energy (ΔG H*) on oxygen atom in the O S O group. As a result, B-BTDO-DT exhibits an outstanding visible light induced photocatalytic H 2 production rate of 156.6 μmol h−1 using 30 mg catalyst without Pt cocatalyst, which is 4.5 times higher than that of B-BTDO. And the H 2 production rate of B-BTDO-DT is further improved to be 259.8 μmol h−1 with 2.0 wt% Pt as co-catalyst. The present work may open a new direction for the design of conjugated polymer based photocatalysts with high photocatalytic activities. A novel thienyl-fused Dibenzothiophene-S,S-dioxide (BTDO) building block (BTDO-DT) is prepared and utilized to synthesize B-BTDO-DT polymer photocatalyst, which exhibits wider visible light absorption region, quicker photogenerated e−/h+ separation and smaller H atom adsorption free energy (ΔG H*) when compared with B-BDTO polymer, resulting in 4.5 times improvement on photocatalytic H 2 production performance. [Display omitted] • Dibenzothiophene-S,S-dioxide is fused by thiophene to prepare B-BTDO-DT polymer. • B-BTDO-DT exhibits narrower band-gap and quicker e−/h+ separation than B-BTDO. • Photocatalytic H 2 production rate of B-BTDO-DT is 4.5 times higher than B-BTDO. [ABSTRACT FROM AUTHOR]

Vanillin is often used in food and medicine because of its unique flavor and pharmacological effects. However, excessive vanillin intake can harm human health; therefore, rapid and simple vanillin detection methods are required. In this study, porphyrin‐based conjugated microporous polymer‐grafted graphene (CMP‐rGO) was synthesized via the Sonogashira–Hagihara coupling reaction and assembled into an electrochemical sensor for vanillin detection. Due to the enhanced electrical conductivity and electrocatalytic characteristics of CMP‐rGO, the sensor demonstrated a low detection limit of 0.07 μM and a broad response range of 0.08–20 μM. Furthermore, this reusable sensor exhibited acceptable recoveries when evaluating vanillin in pharmaceuticals and human serum. This study offers technological assistance for the rapid detection of vanillin in pharmaceuticals and broadens the application of CMP‐rGO. [ABSTRACT FROM AUTHOR]

Conjugated polymers are emerging as competitive candidates for organic thermoelectrics (OTEs). However, to make the device truly pervasive, both p‐ and n‐type conjugated polymers are essential. Despite great efforts, no n‐type equivalents to the p‐type benchmark PEDOT:PSS exist to date mainly due to the low electrical conductivity (σ). Herein, a near‐amorphous n‐type conjugated polymer, namely pDFSe, is reported with high σ by achieving the synergy between charge transport and doping efficiency. The polymer pDFSe is synthesized based on an acceptor‐triad moiety of diketopyrrolopyrrole‐difluorobenzoselenadiazole‐diketopyrrolopyrrole (DFSe), which has the noncovalently‐fused‐ring structure to reinforce the backbone rigidity. Furthermore, an axisymmetric thiophene‐selenophene‐thiophene donor is introduced, which enables the formation of near‐amorphous microstructures. The above merits ensure good doping efficiency without scarifying efficient intrachain charge‐carrier transport. Thus, pDFSe‐based n‐type transistors exhibit high electron mobility up to 6.15 cm2 V−1 s−1, much higher than its reference polymer pDSe without the noncovalently‐fused‐ring structure (0.77 cm2 V−1 s−1). Further upon n‐doping, pDFSe demonstrates excellent σ of 62.6 S cm−1 and maximum power factor of 133.1 μW m−1 K−2, which are among the highest values reported for solution‐processed n‐type polymers. The results demonstrate the great potential of near‐amorphous n‐type conjugated polymers with noncovalently‐fused‐ring structure for the next‐generation OTEs. [ABSTRACT FROM AUTHOR]

The document is a contents list for the journal "Chemical Communications" published in 2024. It includes articles on various topics such as photocatalysis, Raman imaging, glycosylation, and catalysis. The journal is published by The Royal Society of Chemistry, a leading chemistry community. The document provides a list of articles and authors, allowing library patrons to quickly identify articles of interest for their research. [Extracted from the article]

Photodetectors are a key sensing component in enabling emerging technologies. For weak light detection, phototransistors with high responsivity are needed. Furthermore, the ability to fabricate phototransistors using solution processing techniques will enable new form factors, including flexible and large‐area devices. In this work, a novel approach for synthesizing a photosensitive organic/inorganic hybrid semiconducting thin film through solution processing is introduced. The approach involves hierarchical patterning of semiconducting carbon nanotubes (CNTs) with poly(3‐hexylthiophene‐2,5‐dyl) (P3HT) through solution‐phase heterogeneous crystallization. The fabricated hybrid phototransistors are qualified through electrical testing at varied illumination profiles within the visible light range. At a wavelength of 470 nm with an optical excitation power of 0.37 µW cm−2, the device exhibits photoresponsivity of 3.53 × 105 AW−1, surpassing other solution‐processed, non‐lead‐containing devices in the literature. The optical response extends from both photogating (low excitation power) and photon‐induced carrier generation (high excitation power). The detectivity of the device is ≈8.7 × 1010 Jones. The transient response includes a rise time of 100 ms and a fall time of 200 ms which is similar to the metrics of other low‐dimensional photodetectors. These findings highlight the prospects of the solution‐processed P3HT/semi‐CNT hybrid platform for advanced photodetection applications with flexible and large‐area form factors. [ABSTRACT FROM AUTHOR]

The document is a contents list for the journal "Green Chemistry," published by The Royal Society of Chemistry. It highlights the articles and papers featured in the current issue, covering a range of topics related to sustainable chemistry and green technologies. The articles include research on bio-based polymers, nitrogen fixation strategies, carbon aerogels for energy storage, and the use of ionic liquids in new energy and biotechnologies. The journal aims to provide cutting-edge research for a greener and more sustainable future. [Extracted from the article]

Recent progress in conjugated polymer photocatalysts has opened avenues for enhancing photocatalytic hydrogen production (PHP) activity through structural design. This study highlights the impact of the acceptor-to-donor feed ratio on PHP activity in copolymers, influencing their energy level structures. Five conjugated porous polymers (CPPs) were synthesized by adjusting the acceptor-to-donor molar ratio. Notably, at a 2:1 acceptor-to-donor ratio, the polymer demonstrated a high hydrogen evolution rate (HER) of 61.9 mmol g−1 h−1 under full arc irradiation without co-catalysts and an apparent quantum yield (AQY) of 7.77% at 475 nm. However, further increasing the proportion of the donor unit in the copolymers decreases their HER. Experiments and theoretical simulation characterized that the feed ratios effectively tune the polymer's molecular structure, hydrophilicity, band gap, and the generation and transport efficiency of photo-induced charge carriers, ultimately affecting the hydrogen production kinetics and efficiency. This research demonstrates that tuning the band structure and chemical compositions of CPPs through statistical copolymerization significantly impacts their PHP activity. [Display omitted] • Conjugated porous polymers (CPPs) with donor-acceptor type were prepared as photocatalysts. • PProDOT-didecyl was used as the donor unit to tune the energy levels of the CPPs. • BS-4 shows an impressive hydrogen evolution rate of 61.9 mmol g−1 h−1 under full arc free of co-catalyst. • The optimum donor-to-acceptor ratio is crucial for improved photocatalytic activity. [ABSTRACT FROM AUTHOR]

Discovering a competent charge transport layer promoting charge separation in photoelectrodes is a perpetual pursuit in photoelectrochemical (PEC) water splitting to achieve high solar‐to‐hydrogen (STH) conversion efficiency. Here, a conjugated polythiophene framework (CPF‐TTB) on Ta3N5 is elaborately electropolymerized, substantiating the hole transport behavior in their heterojunction. Tailored band structures of the CPF‐TTB/Ta3N5 reinforce the separation of photogenerated carriers, elevating a fill factor of the photoanode modified with a cocatalyst. The enhanced hole extraction enables the NiFeOx/CPF‐TTB/Ta3N5/TiN photoanode to generate a remarkable water oxidation photocurrent density of 9.12 mA cm−2 at 1.23 V versus the reversible hydrogen electrode. A tandem device combining the photoanode with a perovskite/Si solar cell implements an unbiased solar water splitting with a STH conversion efficiency of 6.26% under parallel illumination mode. This study provides novel strategies in interface engineering for metal nitride‐based photoelectrodes, suggesting a promise of the organic–inorganic hybrid photoelectrode for high‐efficiency PEC water splitting. [ABSTRACT FROM AUTHOR]

A conjugated polymer, P4TTD-DPP, based on tetra-fused isoindigo-alt-diketopyrrolopyrrole, has been synthesized as a photothermal therapeutic nanotransducer within the near-infrared-II (NIR-II) window. P4TTD-DPP exhibits a notable mass extinction coefficient of 62.8 L g−1 cm−1 at 1064 nm. Additionally, P4TTD-DPP nanoparticles demonstrate remarkable photothermal conversion efficiency of 91.5% at 1064 nm and exhibit excellent anticancer efficacy under photothermal conditions. [ABSTRACT FROM AUTHOR]

Conjugated polymers with integrating properties of delayed fluorescence and photovoltaic responses simultaneously are scarcely reported due to the generally contradictory requirements for molecular structures to achieve the two properties. Herein, an O‐B(F)←N functionalized fused unit (M) with multiple resonance features, small energy gap between lowest singlet excited state (S1) and triplet excited state (T1) (ΔEST = 0.23 eV), and delayed fluorescence (τD = 0.75 µs), is designed. Selecting three benzodithiophene (BDT) derivatives as co‐units to copolymerize with M, leading to a series of O‐B(F)←N embedded polymers also maintaining delayed fluorescence (τD = 0.4–0.5 µs). Moreover, p‐type semiconductor characteristics are tested for these polymers with hole mobilities in the range of 10−6–10−5 cm2/Vs. Devices with obviously photovoltaic responses are prepared using these polymers as donors and Y6 as the acceptor, affording a preliminary efficiency of 5.05%. This work successfully demonstrates an effective strategy to design conjugated polymers with integrating properties of delayed fluorescence and photovoltaic performance simultaneously by introducing O‐B(F)←N functional groups to polymer backbones. [ABSTRACT FROM AUTHOR]

Stretchable conjugated polymers with conjugation break spacers (CBSs) synthesized via random terpolymerization have gained considerable attention because of their efficacy in modulating mobility and stretchability. This study incorporates a series of dianhydrohexitol diastereomers of isosorbide (ISB) and isomannide (IMN) units into the diketopyrrolopyrrole‐based backbone as CBSs. It is found that the distorted CBS (IMN) improves the mobility–stretchability properties of the polymer with a highly coplanar backbone, whereas the extended CBS (ISB) enhances those of the polymer with a noncoplanar backbone. Additionally, the different configurations of ISB and IMN sufficiently affect the solid‐state packing, aggregation capabilities, crystallographic parameters, and mobility–stretchability properties of the polymer. The IMN‐based polymers exhibit the highest mobility of 1.69 cm2 V−1 s−1 and crystallinity retentions of (85.7, 78.6)% under 20% and 60% strains, outperforming their ISB‐based or unmodified counterparts. The improvement is correlated with a robust aggregation capability. Furthermore, the CBS content affects aggregation behavior, notably affecting mobility. This result indicates that incorporating CBSs into the polymer can enhance backbone flexibility via movement and rotation of the CBS without affecting the crystalline regions. [ABSTRACT FROM AUTHOR]

This article from the Chinese Journal of Chemistry introduces a new member of the editorial board, Shaowei Shi, who is a professor at Beijing University of Chemical Technology. The article provides information about Shi's education, experience, and awards. It also highlights Shi's favorite area of chemistry, which is reconfigurable structured liquids. The article explains how these liquids can be structured through the interfacial assembly and jamming of nanoparticles, allowing for responsiveness and malleability. The concept of nanoparticle surfactants is also discussed, which enables the introduction of chemical functionality and takes advantage of the inherent functionality of nanoparticles. The article emphasizes the generality and potential applications of this concept. [Extracted from the article]

There is a clearly demonstrated relationship between the microstructure, processing and resulting optoelectronic properties of conjugated polymers. Here, we exploited this relationship by exposing polyfluorene thin films to various solvent vapors via confined-solvent vapor annealing to optimize their microstructure, with the final goal being to enhance their emission properties. Our results have demonstrated enlargements in photoluminescence intensity of up to 270%, 258% and 240% when thin films of polyfluorenes of average molecular weights of 105,491 g/mol, 63,114 g/mol and 14,000 g/mol, respectively, experienced increases in their β-phase fractions upon processing. [ABSTRACT FROM AUTHOR]

Conjugated polymers consist of complex backbone structures and side‐chain moieties to meet various optoelectronic and processing requirements. Recent work on conjugated polymers has been devoted to studying the mechanical properties and developing new conjugated polymers with low modulus and high‐crack onset strain, while the thin film mechanical stability under long‐term external tensile strain is less investigated. Here we performed direct mechanical stress relaxation tests for both free‐standing and thin film floated on water surface on both high‐Tg and low‐Tg conjugated polymers, as well as a reference nonconjugated sample, polystyrene. We measured thin films with a range of film thickness from 38 to 179 nm to study the temperature and thickness effect on thin film relaxation, where an apparent enthalpy–entropy compensation effect for glassy polymer PS and PM6 thin films was observed. We also compared relaxation times across three different conjugated polymers and showed that both crystalline morphology and higher modulus reduce the relaxation rate besides higher glass transition temperature. Our work provides insights into the mechanical creep behavior of conjugated polymers, which will have an impact on the future design of stable functional organic electronics. [ABSTRACT FROM AUTHOR]

The doping levels of conjugated polymers significantly influence their conductivity, energetics, and optical properties. Recently, a highly conductive n‐doped polymer called poly (3,7‐dihydrobenzo[1,2‐b:4,5‐b′]difuran‐2,6‐dione) (poly(benzodifurandione), n‐PBDF) is discovered, opening new possibilities for n‐type conducting polymers in printed electronics and other fields. Controlling the doping level of n‐PBDF is of great interest due to its wide range of potential applications. Here controlled dedoping and redoping of n‐PBDF is reported and a mechanistic understating of such a process is provided. Dedoping occurs through electron transfer and proton capture, wherein the ionic dopants, tris(4‐bromophenyl)ammoniumyl hexachloroantimonate (Magic Blue), exhibit efficient proton capture ability and stronger interaction with n‐PBDF, resulting in high dedoping efficiency. Moreover, chemically dedoped PBDF can be redoped using various proton‐coupled electron transfer agents. By manipulating the doping levels of n‐PBDF thin films, ranging from highly doped to dedoped states, the system demonstrates controllable conductivity in five orders of magnitude, adjustable optical properties, and energetics. As a result, these characteristics demonstrate the potential applications of n‐PBDF in organic electrochemical transistors and thermoelectrics. [ABSTRACT FROM AUTHOR]

Preparing well-ordered nanotubes on material surface is fundamental for a huge number of applications. Natural surfaces and theoretical approaches show that porous structures such as nanotubes are key parameters for both surface hydrophobicity and water adhesion. Here, a very easy soft-template electropolymerization approach is used to form nanotubes. A solvent of low water-solubility (dichloromethane) is mixed to water in the presence of a surfactant electrolyte for stabilizing the micelles formed in solution. The monomers investigated are thiophene and carbazole derivatives, and are all fully conjugated for favoring the deposition versus polymerization. Indeed, in all the electrodeposited films, the monomer is mostly present as confirmed by cyclic voltammetry. The key parameters in the resulting nanotubes is the monomer structure because a preferential growth is necessary and this one is induced here especially by π-stacking interactions in the direction perpendicular to monomer. The surfaces composed of nanoparticles or nanotubes are the most hydrophobic with an apparent contact angle up to 130.9° accompanied with strong water adhesion, as reported on gecko foot or rose petal. [ABSTRACT FROM AUTHOR]

Triazine-based conjugated polymers with high electron transfer efficiency obtained the enhanced photocatalytic activities by D-A polarization for degradation of BPA and benzene pollutants. [Display omitted] • Triazine-based D-A conjugated polymers were fabricated by simple Schiff-base reaction. • The separation and transfer of photogenerated carriers is improved by D-A configuration regulation. • The π-conjugated skeleton facilitates the adsorption and activation of aromatic pollutant molecules. • Tr-BTh exhibited complete photocatalytic degradation of 50 ppm BPA in 40 min. Photocatalysis is a green and environmentally friendly method for degrading dangerous and nonbiodegradable pollutants. In this study, a sequence of metal-free triazine-based electronic donor–acceptor (D-A) conjugated polymers Tr-X (X = Th, BT, BTh) were prepared by D-A configuration regulation between triazine (Tr) and monomers containing N and S, such as thiophene (Th), bithiophene (BTh) and benzothiadiazole (BT) units, for the photocatalytic degradation of bisphenol A (BPA) and benzene contaminants in water under visible light. Among these, Tr-BTh exhibited complete photocatalytic degradation owing to its excellent D-A configuration. Moreover, the N and S atoms, which are rich in triazine and thiophene units, serve as highly dispersed reactive sites. The separation and transfer of photogenerated carriers can be further improved by expanding the light-absorption range of polymers. In addition, the polymers showed good adsorption for BPA and other aromatic organic pollutants through π-π interaction and surface hydrogen bonding, which provides a facile strategy for efficient polymer-based photocatalysts for water purification. [ABSTRACT FROM AUTHOR]

Water‐dispersible fluorescent nano‐/microspheres have been widely used as fluorescent probes in many fields. In this paper, aldehyde‐functionalized fluorescent micelles are synthesized by self‐assembly of end‐modified hyperbranched poly(m‐phenyleneethynylene‐alter‐p‐phenyleneethynylene)(hb‐PMPE). First, hb‐PMPE with ‐Br end‐groups(hb‐PMPE‐Br) is obtained by the polymerization of AB2 monomer PhBr2–C≡C–Ph–C≡CH, then the reaction of hb‐PMPE‐Br with 4‐ethynylbenzaldehyde (EBA) gives end aldehyde‐functionalized hyperbranched polymer hb‐PMPE‐CHO. Hence, hb‐PMPE‐CHO is reacted with aminooxy methoxypolyethylene glycol‐2000 (NH2O‐MPEG2000) to link poly(ethylene glycol) (PEG) chains to the ends of hb‐PMPE‐CHO with partial residual aldehyde end‐groups, resulting in aldehyde‐functionalized amphiphilic polymer hb‐PMPE‐PEG. Fluorescent micelles with aldehyde‐containing fluorescent hb‐PMPE core and PEG shell are obtained by self‐assembling hb‐PMPE‐PEG in water. The micelle diameter is determined by the PEG content in hb‐PMPE‐PEG, which can be controlled by the reaction weight ratio of NH2O‐MPEG2000/hb‐PMPE‐CHO. When the ratio of NH2O‐MPEG2000/hb‐PMPE‐CHO > 0.75/1, micelles with a diameter < 50 nm are obtained. The water dispersion of hb‐PMPE‐PEG‐1/2 micelles (28.9 nm) emits bright green fluorescence with λmax ≈ 490 nm under UV irradiation, and the emission intensity increases with increasing concentration. [ABSTRACT FROM AUTHOR]

For advancing next‐generation optoelectronics, a versatile strategy for fabricating π‐conjugated polymer (π‐CP)/chiral‐small molecule (SM) hybrid films through co‐crystallization‐mediated chirality transfer is reported. The transfer of optical chirality from 1,1′‐binaphthyl–2,2′‐diamine (BN), a representative chiral inducer SM, to thin films of various achiral π‐CPs, including non‐fluorene π‐CPs, is achieved by simply blending the π‐CPs with BN using aromatic organic solvents. The resulting π‐CP/chiral‐SM hybrid films exhibit chiroptical responses at the main electronic absorption bands of various π‐CPs. Studies of the morphology, crystalline structure, and phase‐separation structure of a representative hybrid system of poly(3‐hexylthiophene) (P3HT) and BN reveal that these hybrid films exhibit a characteristic lamellar structure where the π‐CPs co‐crystallize with chiral BN molecules, facilitated by aromatic solvent‐assisted intermolecular π–π interactions. In‐depth photophysical analysis suggests that BN molecules co‐crystallized in the P3HT lamellar structure induce asymmetrically misaligned transition dipoles along the P3HT conjugated backbone, transferring optical chirality from BN to P3HT under circularly polarized light illumination. As a proof‐of‐concept, chiroptical photodiodes based on π‐CP/chiral‐SM hybrid films and printed micropatterns, exhibiting a distinguishable photocurrent response depending on the direction of circularly polarized light are successfully demonstrated. [ABSTRACT FROM AUTHOR]