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.

Strengthening tumor cellular adhesion through regulating the concentration of extracellular Ca2+ is highly challenging and promising for antimetastasis. Herein, a pH-responsive conjugated polymer-calcium composite nanoparticle (PFV/CaCO3/PDA@PEG) is developed for calcium-mediated cell adhesion enhancement-based antimetastasis and reactive oxygen species (ROS)-triggered calcium overload and photodynamic therapy (PDT) synergistic tumor treatment. PFV/CaCO3/PDA@PEG is mainly equipped with conjugated poly(fluorene-co-vinylene) (PFV-COOH)-composited CaCO3 nanoparticles, which can be rapidly decomposed under the tumor acidic microenvironment, effectively releasing Ca2+ and the photosensitizer PFV-COOH. The high extracellular Ca2+ concentration facilitates the generation of dimers between two adjacent cadherin ectodomains, which greatly enhances cell-cell adhesion and suppresses tumor metastasis. The inhibition rates are 97 and 87% for highly metastatic tumor cells 4T1 and MCF-7, respectively. Such a well-designed nanoparticle also contributes to realizing PDT, mitochondrial dysfunction, and ROS-triggered Ca2+ overload synergistic therapy. Furthermore, PFV/CaCO3/PDA@PEG displayed superior in vivo inhibition of 4T1 tumor growth and demonstrated a marked antimetastatic effect by both intravenous and intratumoral injection modes. Thus, this study provides a powerful strategy for calcium-mediated metastasis inhibition for tumor therapy.

Lithiated Cu current collectors with a lean Li supply have been extensively explored as prospective composite anodes for constructing lithium metal batteries (LMBs) but suffer from low Coulombic efficiencies (CE) and uncontrollable dendrite growth. Herein, two hexaazanonaphthalene (HATN)-based compounds comprising rich conjugated aromatic rings and redox-active C═N groups are synthesized and exploited to modify the Cu surface for mediating smooth Li plating/stripping. Compared to the HATN compound interlinked through flexible sigma bonds, the one conjugated through dual sp2-carbon manifests a more rigid backbone, improved electric conductivity, and enhanced mesoporosity. As a result, Cu electrodes modified with the latter demonstrate enhanced CE and suppressed dendrites in both half and symmetric cells, apart from a stable operation over 250 cycles in the LiFePO4 full cells with a capacity retention of 94.9% at 1 C. This study signifies the tailoring of intramolecular conjugation and chain configuration of lithiophilic macromolecules to facilitate reversible Li deposition on Cu for achieving high-performance LMBs.

Introduction of amidine groups within the side chains of a conjugated polyfluorene was carried out using copper-catalyzed azide-alkyne cycloaddition. The resulting polymer was shown to form strong supramolecular interactions with the sidewalls of single-walled carbon nanotubes (SWNTs), forming polymer-nanotube complexes that exhibited solubility in various organic solvents. It was shown that the polymer-SWNT complexes were responsive to CO2, where the amidine groups formed amidinium bicarbonate salts upon CO2 exposure, causing the polymer-SWNT complexes to precipitate. This reaction could be reversed by bubbling N2 through the solution, which caused the polymer-SWNT complexes to redissolve. Incorporation of the polymer-SWNT complexes within thin-film transistor (TFT) devices as the active layer resulted in a CO2-responsive TFT sensor. It was found that the sensory device underwent a reversible shift in its threshold voltage from 5 to -1 V as well as a 1 order of magnitude decrease in its on-current upon exposure to CO2. This work shows that conjugated polymer-wrapped SWNTs having sensory elements within the polymer side chain can be used as the active layer within functional SWNT-based TFT sensors.

Polymer-wrapped single-walled carbon nanotubes (SWNTs) are a potential method for obtaining high-purity semiconducting (sc) SWNT solutions. Conjugated polymers (CPs) can selectively sort sc-SWNTs with different chiralities, and the structure of the polymer side chains influences this sorting capability. While extensive research has been conducted on modifying the physical, optical, and electrical properties of CPs through side-chain modifications, the impact of these modifications on the sorting efficiency of sc-SWNTs remains underexplored. This study investigates the introduction of various conjugated side chains into naphthalene diimide-based CPs to create a biaxially extended conjugation pattern. The CP with a branched conjugated side chain (P3) exhibits reduced aggregation, resulting in improved wrapping ability and the formation of larger bundles of high-purity sc-SWNTs. Grazing incidence X-ray diffraction analysis confirms that the potential interaction between sc-SWNTs and CPs occurs through π-π stacking. The field-effect transistor device fabricated with P3/sc-SWNTs demonstrates exceptional performance, with a significantly enhanced hole mobility of 4.72 cm2 V-1 s-1 and high endurance/bias stability. These findings suggest that biaxially extended side-chain modification is a promising strategy for improving the sorting efficiency and performance of sc-SWNTs by using CPs. This achievement can facilitate the development of more efficient and stable electronic devices.

The photosynaptic transistor stands as a promising contender for overcoming the von Neumann bottleneck in the realm of photo-communication. In this context, photonic synaptic transistors is developed through a straightforward solution process, employing an organic semiconducting polymer with pendant-naphthalene-containing side chains (PDPPNA) in combination with ligand-density-engineered CsPbBr3 perovskite quantum dots (PQDs). This fabrication approach allows the devices to emulate fundamental synaptic behaviors, encompassing excitatory postsynaptic current, paired-pulse facilitation, the transition from short-to-long-term memory, and the concept of \"learning experience.\" Notably, the phototransistor, incorporating the blend of the PDPPNA and CsPbBr3 PQDs washed with ethyl acetate, achieved an exceptional memory ratio of 104. Simultaneously, the same device exhibited an impressive paired-pulse facilitation ratio of 223% at a moderate operating voltage of -4 V and an extraordinarily low energy consumption of 0.215 aJ at an ultralow operating voltage of -0.1 mV. Consequently, these low-voltage synaptic devices, constructed with a pendant side-chain engineering of organic semiconductors and a ligand density engineering of PQDs through a simple fabrication process, exhibit substantial potential for replicating the visual memory capabilities of the human brain.

Organic solar cells (OSCs) are considered a very promising technology to convert solar energy to electricity and a feasible option for the energy market because of the advantages of light weight, flexibility, and roll-to-roll manufacturing. They are mainly characterized by a bulk heterojunction structure where a polymer donor is blended with an electron acceptor. Their performance is highly affected by the design of donor-acceptor conjugated polymers and the choice of suitable acceptor. In particular, benzotriazole, a typical electron-deficient penta-heterocycle, has been combined with various donors to provide wide bandgap donor polymers, which have received a great deal of attention with the development of non-fullerene acceptors (NFAs) because of their suitable matching to provide devices with relevant power conversion efficiency (PCE). Moreover, different benzotriazole-based polymers are gaining more and more interest because they are considered promising acceptors in OSCs. Since the development of a suitable method to choose generally a donor/acceptor material is a challenging issue, this review is meant to be useful especially for organic chemical scientists to understand all the progress achieved with benzotriazole-based polymers used as donors with NFAs and as acceptors with different donors in OSCs, in particular referring to the PCE.

Conjugated polymers (CPs)-based near-infrared phototheranostics are receiving increasing attention due to their high molar extinction coefficient, wide emission wavelength, easy preparation and excellent biocompatibility. Herein, several new conjugated polymers with D2-D1-A structures were easily prepared through one-pot coupling using triphenylamine (D2) as well as thiophenes (D1) as electron donors and benzothiadiazole (A) as electron acceptors. Interesting, their optical performance and power conversion efficiency could be tuned by side chains on thiophenes (D1). The introduction of ethylenedioxy into D1 as side chain significantly improves fluorescence imaging brightness, photothermal conversion efficiency and hydrophilicity, and extends emission wavelength, which are beneficial for phototheranostic. The side chain modification provides new opportunity to design efficient phototheranostics without construction new fluorescent skeletons.

The solution aggregation structure of conjugated polymers is crucial to the morphology and resultant optoelectronic properties of organic electronics and is of considerable interest in the field. Precise characterizations of the solution aggregation structures of organic photovoltaic (OPV) blends and their temperature-dependent variations remain challenging. In this work, the temperature-dependent solution aggregation structures of three representative high-efficiency OPV blends using small-angle X-ray/neutron scattering are systematically probed. Three cases of solution processing resiliency are elucidated in state-of-the-art OPV blends. The exceptional processing resiliency of high-efficiency PBQx-TF blends can be attributed to the minimal changes in the multiscale solution aggregation structure at elevated temperatures. Importantly, a new parameter, the percentage of acceptors distributed within polymer aggregates (Ф), for the first time in OPV blend solution, establishes a direct correlation between Ф and performance is quantified. The device performance is well correlated with the Kuhn length of the cylinder related to polymer aggregates L1 at the small scale and the Ф at the large scale. Optimal device performance is achieved with L1 at ≈30 nm and Ф within the range of 60 ± 5%. This study represents a significant advancement in the aggregation structure research of organic electronics.

Conjugated polymers with ethylene glycol-type side chains are commonly used as channel materials in organic electrochemical transistors (OECTs). To improve the performance of these materials, new chemical structures are often created through synthetic routines. Herein, we demonstrate that the OECT performance of these polymers can also be improved by changing their density-of-state (DOS) profile through solvent engineering. Depending on the solvent polarity, it solvates the backbone and side chains of the conjugated polymer differently, leading to differences in molecule orientation, π-stacking paracrystallinity, and film defects, such as grain boundaries and pinholes. This then results in a change in the DOS profile of the polymer. A more intense and narrow-width DOS distribution is usually observed in organic films with an \"edge on\" orientation and fewer film defects, while films with a \"face on\" orientation and apparent defects show a broadened DOS profile. The OECT devices that use the polymer film with a more intense and narrow-width DOS profile exhibit a better-normalized transconductance and figure-of-merit μC* than those with a broadened DOS profile (0.74 to 4.29 S cm-1 and 3.5 to 14.3 F cm-1 V-1 s-1). This study provides useful insights into how the DOS profile affects the mixed ionic-electronic conduction performance and presents a new avenue for improving n-type OECT materials.