Solution-Processable Indenofluorenes on Polymer Brush Interlayer: Remarkable N-Channel Field-Effect Transistor Characteristics under Ambient Conditions.

The development of solution-processable n-type molecular semiconductors that exhibit high electron mobility (µe ≥ 0.5 cm2/(V·s)) under ambient conditions, along with high current modulation (Ion/Ioff ≥ 106-107) and near-zero turn on voltage (Von) characteristics, has lagged behind that of other semiconductors in organic field-effect transistors (OFETs). Here, we report the design, synthesis, physicochemical and optoelectronic characterizations, and OFET performances of a library of solution-processable, low-LUMO (-4.20 eV) 2,2'-(2,8-bis(3-alkylthiophen-2-yl)indeno[1,2-b]fluorene-6,12-diylidene)dimalononitrile small molecules, ß,ß'-Cn-TIFDMTs, having varied alkyl chain lengths (n = 8, 12, 16). An intriguing correlation is identified between the solid-isotropic liquid transition enthalpies and the solubilities, indicating that cohesive energetics, which are tuned by alkyl chains, play a pivotal role in determining solubility. The semiconductors were spin-coated under ambient conditions on densely packed (grafting densities of 0.19-0.45 chains/nm2) ultrathin (∼3.6-6.6 nm) polystyrene-brush surfaces. It is demonstrated that, on this polymer interlayer, thermally induced dispersive interactions occurring over a large number of methylene units between flexible alkyl chains (i.e., zipper effect) are critical to achieve a favorable thin-film crystallization with a proper microstructure and morphology for efficient charge transport. While C8 and C16 chains show a minimal zipper effect upon thermal annealing, C12 chains undergo an extended interdigitation involving ∼6 methylene units. This results in the formation of large crystallites having lamellar stacking ((100) coherence length ∼30 nm) in the out-of-plane direction and highly favorable in-plane π-interactions in a slipped-stacked arrangement. Uninterrupted microstructural integrity (i.e., no face-on (010)-oriented crystallites) was found to be critical to achieving high mobilities. The excellent crystallinity of the C12-substituted semiconductor thin film was also evident in the observed crystal lattice vibrations (phonons) at 58 cm-1 in low-frequency Raman scattering. Two-dimensional micrometer-sized (∼1-3 µm), sharp-edged plate-like grains lying parallel with the substrate plane were observed. OFETs fabricated by the current small molecules showed excellent n-channel behavior in ambient with µe values reaching ∼0.9 cm2/(V·s), Ion/Ioff ∼ 107-108, and Von ≈ 0 V. Our study not only demonstrates one of the highest performing n-channel OFET devices reported under ambient conditions via solution processing but also elucidates significant relationships among chemical structures, molecular properties, self-assembly from solution into a thin film, and semiconducting thin-film properties. The design rationales presented herein may open up new avenues for the development of high-electron-mobility novel electron-deficient indenofluorene and short-axis substituted donor-acceptor π-architectures via alkyl chain engineering and interface engineering.

Simplified Y6-Based Nonfullerene Acceptors: In-Depth Study on Molecular Structure-Property Relation, Molecular Dynamics Simulation, and Charge Dynamics.

Two new Y6 derivatives of symmetrical YBO-2O and asymmetrical YBO-FO nonfullerene acceptors (NFAs) are prepared with a simplified synthetic procedure by incorporating octyl and fluorine substituents onto the terminal 2-(3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile (INCN) moiety. By moving the alkyl substituents on the Y6 core to the terminal INCN moiety, the lowest unoccupied molecular orbital of the YBO NFAs increases without decreasing solubility, resulting in high open-circuit voltages of the devices. Molecular dynamics simulation shows that YBO-2O/-FO preferentially form core-core and terminal-terminal dimeric interactions, demonstrating their tighter packing structure and higher electron mobility than Y6, which is consistent with 2D grazing incidence X-ray scattering and space charge limited current measurements. In blend films, the hole transfer (HT) from YBO-2O/-FO to the polymer donor PM6 is studied in detail by transient absorption spectroscopy, demonstrating efficient HT from YBO-FO to PM6 with their suitable energy level alignment. Despite the simplified synthesis, YBO-FO demonstrates photovoltaic performance similar to that of Y6, exhibiting a power conversion efficiency of 15.01%. Overall, this design strategy not only simplifies the synthetic procedures but also adjusts the electrical properties by modifying the intermolecular packing and energy level alignment, suggesting a novel simplified molecular design of Y6 derivatives.

Alkyl Chain Engineering of Low Bandgap Non-Fullerene Acceptors for High-Performance Organic Solar Cells: Branched vs. Linear Alkyl Side Chains.

In this work, we report the synthesis and photovoltaic properties of IEBICO-4F, IEHICO-4F, IOICO-4F, and IDICO-4F non-fullerene acceptors (NFAs) bearing different types of alkyl chains (2-ehtylhexyl (EH), 2-ethylbutyl (EB), n-octyl (O), and n-decyl (D), respectively). These NFAs are based on the central indacenodithiophene (IDT) donor core and the same terminal group of 2-(5,6-difluoro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile (IC-2F), albeit with different side chains appended to the thiophene bridge unit. Although the side chains induced negligible differences between the NFAs in terms of optical band gaps and molecular energy levels, they did lead to changes in their melting points and crystallinity. The NFAs with branched alkyl chains exhibited weaker intermolecular interactions and crystallinity than those with linear alkyl chains. Organic solar cells (OSCs) were fabricated by blending these NFAs with the p-type polymer PTB7-Th. The NFAs with appended branched alkyl chains (IEHICO-4F and IEBICO-4F) possessed superior photovoltaic properties than those with appended linear alkyl chains (IOICO-4F and IDICO-4F). This result can be ascribed mainly to the thin-film morphology. Furthermore, the NFA-based blend films with appended branched alkyl chains exhibited the optimal degree of aggregation and miscibility, whereas the NFA-based blend films with appended linear alkyl chains exhibited higher levels of self-aggregation and lower miscibility between the NFA molecule and the PTB7-Th polymer. We demonstrate that changing the alkyl chain on the π-bridging unit in fused-ring-based NFAs is an effective strategy for improving their photovoltaic performance in bulk heterojunction-type OSCs.

Antibacterial Theranostic Agents with Negligible Living Cell Invasiveness: AIE-Active Cationic Amphiphiles Regulated by Alkyl Chain Engineering.

To address the threat of bacterial infection in the following post-antibiotic era, developing effective antibacterial approaches is of utmost urgency. Theranostic medicine integrating diagnosis and therapy is a promising protocol to fight against pathogenic bacteria. But numerous reported antibacterial theranostic materials are disclosed to be trapped in the excessive invasiveness to living mammal cells, leading to false positives and possible biosafety risks. Herein, a series of cationic pyridinium-substituted phosphindole oxide derivatives featuring aggregation-induced emission are designed, and alkyl chain engineering is conducted to finely tune their hydrophobicity and investigate their bioaffinity preference for living mammal cells and pathogenic bacteria. Most importantly, an efficient theranostic agent (PyBu-PIO) is acquired that is free from living cell invasiveness with negligible cytotoxicity and yet holds a good affinity for Gram-positive bacteria, including drug-resistant strains, with a superior inactivating effect. Externally applying PyBu-PIO onto Gram-positive bacteria-infected skin wounds can achieve creditable imaging effects and successfully accelerate the healing processes with reliable biosafety. This work proposes living cell invasiveness as a criterion for antibacterial theranostic materials and provides important enlightenment for the design of antibacterial theranostic materials.

Switching Chirophilic Self-assembly: From meso-structures to Conglomerates in Liquid and Liquid Crystalline Network Phases of Achiral Polycatenar Compounds.

Spontaneous generation of chirality from achiral molecules is a contemporary research topic with numerous implications for technological applications and for the understanding of the development of homogeneous chirality in biosystems. Herein, a series of azobenzene based rod-like molecules with an 3,4,5-trialkylated end and a single n-alkyl chain involving 5 to 20 aliphatic carbons at the opposite end is reported. Depending on the chain length and temperature these achiral molecules self-assemble into a series of liquid and liquid crystalline (LC) helical network phases. A chiral isotropic liquid (Iso1 [ *] ) and a cubic triple network phase with chiral I23 lattice were found for the short chain compounds, whereas non-cubic and achiral cubic phases dominate for the long chain compounds. Among them a mesoscale conglomerate with I23 lattice, a tetragonal phase (Tetbi ) containing one chirality synchronized and one non-synchronized achiral network, an achiral double network meso-structure with Ia 3 ‾ $\bar 3$ d space group and an achiral percolated isotropic liquid mesophase (Iso1 ) were found. This sequence is attributed to an increasing strength of chirality synchronization between the networks, combined with a change of the preferred mode of chirophilic self-assembly between the networks, switching from enantiophilic to enantiophobic with decreasing chain length and lowering temperature. These nanostructured and mirror symmetry broken LC phases exist over wide temperature ranges which is of interest for potential applications in chiral and photosensitive functional materials derived from achiral compounds.

Fine Tuning of Emission Behavior, Self-Assembly, Anion Sensing, and Mitochondria Targeting of Pyridinium-Functionalized Tetraphenylethene by Alkyl Chain Engineering.

Compared to the many studies that focus on the development of novel molecular frameworks pertaining to functionalized fluorescent materials, there is lesser emphasis on side chains even though they have a significant impact on the properties and applications of fluorescent materials. In this study, a series of pyridinium-functionalized tetraphenylethene salts (TPEPy-1 to TPEPy-4) possessing different alkyl chains are synthesized, and the influence of chain length on their optical performance and applications is thoroughly investigated. By changing the alkyl chain, the fluorogens exhibit opposite emission behavior in aqueous media because of their distinct hydrophobic nature, and their solid-state emission can be fine-tuned from green to red owing to their distinct molecular configuration. In addition, by increasing the chain length, the microstructure of the self-assembled fluorogens converts from microplates to microrods with various emission colors. Moreover, TPEPy-1 exhibits dual-mode fluorescence "turn-on" response toward NO3- and ClO4- in aqueous media because the anions induce the self-assembly of fluorogens. Furthermore, the fluorogens display cellular uptake selectivity while the proper alkyl chain impels the fluorogens to penetrate the cell membrane and accumulate in the mitochondria with high specificity.