Band-like transport in solution-processed perylene diimide dianion films with high Hall mobility.

It is crucial to prepare high-mobility organic polycrystalline film through solution processing. However, the delocalized carrier transport of polycrystalline films in organic semiconductors has rarely been investigated through Hall-effect measurement. This study presents a strategy for building strong intermolecular interactions to fabricate solution-crystallized p-type perylene diimide (PDI) dianion films with a closer intermolecular π-π stacking distance of 3.25 Å. The highly delocalized carriers enable a competitive Hall mobility of 3 cm2 V-1 s-1, comparable to that of the reported high-mobility organic single crystals. The PDI dianion films exhibit a high electrical conductivity of 17 S cm-1 and typical band-like transport, as evidenced by the negative temperature linear coefficient of mobility proportional to T-3/2. This work demonstrates that, as the intermolecular π-π interactions become strong enough, they will display high mobility and conductivity, providing a new approach to developing high-mobility organic semiconductor materials.

Extremely Stable Perylene Bisimide-Bridged Regioisomeric Diradicals and Their Redox Properties.

Excellent stability is an essential premise for organic diradicals to be used in organic electronic and spintronic devices. We have attached two tris(2,4,6-trichlorophenyl)methyl (TTM) radical building blocks to the two sides of perylene bisimide (PBI) bridges and obtained two regioisomeric diradicals (1,6-TTM-PBI and 1,7-TTM-PBI). Both of the isomers show super stability rather than the monomeric TTM under ambient conditions, due to the increased conjugation and the electron-withdrawing effects of the PBI bridges. The diradicals show distinct and reversible multistep redox processes, and a spectro-electrochemistry investigation revealed the generation of organic mixed-valence (MV) species during reduction processes. The two diradicals have singlet ground states, very small singlet-triplet energy gaps (ΔES-T ) and a pure open-shell character (with diradical character y0 =0.966 for 1,6-TTM-PBI and 0.967 for 1,7-TTM-PBI). This work opens a window to developing very stable diradicals and offers the opportunity of their further application in optical, electronic and magnetic devices.

Influence of Interaction between Electrolyte with Side-Chain Free Conjugated Polymer on the Performance of Organic Electrochemical Transistors.

Organic electrochemical transistors (OECTs) offer significant advantages in electrophysiological applications, primarily due to their ability to facilitate ionic-to-electronic conversion and establish a direct interface with the surrounding aqueous environments by using organic mixed ionic-electronic conductors. This study employs a side-chain free n-type conducting polymer, poly(benzodifurandione) (PBFDO), as the channel material in OECTs to scrutinize the interplay between various ion concentrations in electrolytes and the conjugated polymer and to assess their subsequent impact on device performance. Our findings reveal that PBFDO-based OECTs demonstrate superior transfer characteristics, attributed to their high conductivity and remarkable stability in aqueous solutions. Interestingly, the ion concentration does not alter the electronic band structure of PBFDO during the doping process, but a high-salt-concentration electrolyte could accelerate the electrochemical process compared to its counterparts. Furthermore, the diluted solution significantly enhances the surface roughness and decreases the crystalline coherence length of the film compared with concentrated solutions. A quantitative analysis utilizing an electrochemical quartz crystal microbalance discloses that the electrolyte ions penetrate the PBFDO film, inducing the absorption of a fraction of water molecules, which is pronounced in diluted solutions and negligible in their concentrated counterparts. This notable swelling of the polymer in diluted solutions potentially hampers the transport of charge carriers, consequently diminishing the OECT performance. This research elucidates a direct correlation between microstructure alterations and device performance during operation, paving the way for the optimization of ionic and electronic conductivity in polymers to foster the development of high-performance organic electronic devices.

Nanoarchitectonics on Electrosynthesis and Assembly of Conjugated Metallopolymers.

In contrast to edge-on and face-on orientations, end-on uniaxial conjugated polymers have the theoretical possibility of providing a macroscopic crystalline film. However, their fabrication is insurmountable due to sluggishly thermodynamic equilibrium states. Herein, we report the programmatic pathway to fabricate nanoarchitectonics on end-on uniaxial conjugated metallopolymers by surface-initiated simultaneous electrosynthesis and assembly. Self-assembled monolayer (SAM) with bottom-up oriented electroactive molecules as a temple allows orientation, stacking, and reactive addition of monomers triggered by switching alternative redox reactions as well as crystallization of small molecules. Repeating the same reaction can repair the unreactive site on the SAM and dynamically and statistically ensure maximum iterative coverage with ideal linear coefficients between optical or electrical responses and iterative times. The resulting nanoarchitectonics on uniaxially assembled end-on polymers over centimeter-sized areas have a subnanometer-uniform morphology and exhibit ultrahigh modulus as well as an inorganic indium tin oxides and the highest conductance among conjugated molecular monolayers. Their memristive devices provide quantitative electrical and optical responses as a function of molecular length, bias, and iterative junctions. Precise processing of nanoarchitectonics as an electrically assisted assembly or printing technique can present sophisticated optoelectric functions and dimensional batch-to-batch consistency for micro-sized organic materials and electronics.

A theoretical study on π-stacking and ferromagnetism of the perylene diimide radical anion dimer and tetramer.

Ferromagnetism is rare in pure organic materials. Recently, the perylene diimide radical anion (PDI-) salt prepared through solvothermal reduction by hydrazine hydrate has shown room-temperature ferromagnetism in our work [Jiang et al., Adv. Mater., 2022, 34, 2108103]. Based on this, herein we conduct a theoretical study based on density functional theory (DFT) to reveal the stacked geometries between two NH4PDI monomers for low-spin (LS) and high-spin (HS) states and their magnetic exchange interactions (JAB) using Yamaguchi's approximate spin projection. It is observed that the pancake-bonded dimer of NH4PDI is the most stable pimer compared to others on both LS and HS potential energy surfaces. A transition of magnetic properties from strong antiferromagnetic (-1333.9 cm-1) to moderate ferromagnetic (67.0 cm-1) appears after increasing the interplanar distance between monomers and their relative rotation angle to access the HS state. According to energy decomposition analysis, the enhanced hydrogen bond formation and decrease of Pauli repulsion is able to counteract the decrease of attraction induced by electron correlation after accessing the HS state. Stacking patterns of exchange-coupled chain consisting of the NH4PDI tetramer are obtained for the HS state after geometry optimization of the structure constructed by two most stable HS pimers. The exchange interactions (51.8 cm-1, 381.2 cm-1 and 53.2 cm-1) between adjacent NH4PDI monomers are ferromagnetic in the HS state, which is in accordance with the experimentally observed room-temperature ferromagnetism.

Chemical doping of unsubstituted perylene diimide to create radical anions with enhanced stability and tunable photothermal conversion efficiency.

N-doping of perylene diimides (PDIs) to create stable radical anions is significant for harvesting photothermal energy due to their intensive absorption in the near-infrared (NIR) region and non-fluorescence. In this work, a facile and straightforward method has been developed to control the doping of perylene diimide to create radical anions using organic polymer polyethyleneimine (PEI) as a dopant. It was demonstrated that PEI is an effective polymer-reducing agent for the n-doping of PDI toward the controllable generation of radical anions. In addition to the doping process, PEI could suppress the self-assembly aggregation and improve the stability of PDI radical anions. Tunable NIR photothermal conversion efficiency (maximum 47.9%) was also obtained from the radical-anion-rich PDI-PEI composites. This research provides a new strategy to tune the doping level of unsubstituted semiconductor molecules for varying yields of radical anions, suppressing aggregation, improving stability, and obtaining the highest radical anion-based performance.

Correction: lncRNA PSMB8-AS1 promotes colorectal cancer progression through sponging miR-1299 to upregulate ADAMTS5.

This corrects the article DOI: 10.4149/neo_2022_220111N42.

A Nitroxide Radical Conjugated Polymer as an Additive to Reduce Nonradiative Energy Loss in Organic Solar Cells.

Nonfullerene-acceptor-based organic solar cells (NFA-OSCs) are now set off to the 20% power conversion efficiency milestone. To achieve this, minimizing all loss channels, including nonradiative photovoltage losses, seems a necessity. Nonradiative recombination, to a great extent, is known to be an inherent material property due to vibrationally induced decay of charge-transfer (CT) states or their back electron transfer to the triplet excitons. Herein, it is shown that the use of a new conjugated nitroxide radical polymer with 2,2,6,6-tetramethyl piperidine-1-oxyl side groups (GDTA) as an additive results in an improvement of the photovoltaic performance of NFA-OSCs based on different active layer materials. Upon the addition of GDTA, the open-circuit voltage (VOC ), fill factor (FF), and short-circuit current density (JSC ) improve simultaneously. This approach is applied to several material systems including state-of-the-art donor/acceptor pairs showing improvement from 15.8% to 17.6% (in the case of PM6:Y6) and from 17.5% to 18.3% (for PM6:BTP-eC9). Then, the possible reasons behind the observed improvements are discussed. The results point toward the suppression of the CT state to triplet excitons loss channel. This work presents a facile, promising, and generic approach to further improve the performance of NFA-OSCs.

The Multiplicity of π-π Interactions of Fused-Ring Electron Acceptor Polymorphs on the Exciton Migration and Charge Transport.

Efficient long-range exciton migration and charge transport are the key parameters for organic photovoltaic materials, which strongly depend on the molecular stacking modes. Herein, we extracted the stacked structures of the archetype fused-ring electron acceptor molecule, ITIC, based on the information on four polymorphic crystals and investigated the relationship between molecular stacking modes and exciton migration/charge transport properties through the intermolecular Coulomb coupling and charge transfer integral calculation. Experimentally, the thin film texture is crystallized through a post-annealing treatment through grazing-incidence wide-angle X-ray scattering (GIWAXS) measurements, which lead to the enhanced exciton migration through exciton-exciton annihilation in the femtosecond transient absorption (fs-TA) measurements. This work demonstrates the relationship between the molecular arrangement and the exciton migration and electron transport and highlights the significance of optimizing molecular stacking for the development of high-performance electron acceptor materials.

Sulfone-Embedded Heterocyclic Narrowband Emitters with Strengthened Molecular Rigidity and Suppressed High-Frequency Vibronic Coupling.

Sulfone-embedded heterocyclics are of great interest in organic light-emitting diodes (OLEDs), however, exploring highly efficient narrowband emitters based on sulfone-embedded heterocyclics remains challenging. Herein, five emitters with different sulfur valence state and molecular rigidity, namely tP, tCPD, 2tCPD, tPD and tPT, are thoroughly analysed. With restricted twisting of flexible peripheral phenyl by strengthening molecular rigidity, molecular emission spectra can be enormously narrowed. Further, introducing the sulfone group with bending vibration in low-frequency region that suppresses high-frequency vibration, sharp narrow full-widths at half-maximum of 28 and 25 nm are achieved for 2tCPD and tPD, respectively. Maximum external quantum efficiencies of 22.0 % and 27.1 % are successfully realized for 2tCPD- and tPD-based OLED devices. These results offer a novel design strategy for constructing narrowband emitters by introducing sulfone group into a rigid molecular framework.

The Causal Effect of Reproductive Factors on Breast Cancer: A Two-Sample Mendelian Randomization Study.

Several studies have shown that female reproductive factors are associated with breast cancer (BC), but the results differ. We conducted two-sample MR in the present work. The raw data applied in the MR study were all from the Genome-wide association study (GWAS) database. The causal effect of reproductive factors on breast cancer were mainly estimated by the standard inverse variance weighted (IVW) method. Cochran's Q test and I2 statistics were used to assess heterogeneity. The pleiotropy was evaluated by MR-Egger intercept test and MR-PRESSO. Finally, the leave-one-out analysis was performed to evaluate the robustness of the MR results. We found that there was a negative causal effect of the age at last live birth on BC (OR = 0.687, 95%CI = 0.539-0.875, p = 0.002) and positive effect of the age at menopause on BC (OR = 1.054, 95%CI = 1.034-1.075, p = 8.010 × 10-8). Additionally, there were null effects of the age at menarche (OR = 0.977, 95%CI = 0.915-1.043, p = 0.484), the age at first sexual intercourse (OR = 1.053, 95%CI = 0.958-1.157, p = 0.284) and the age at first birth (OR = 0.981, 95%CI = 0.936-1.027, p = 0.404) on BC. All these results were reliable and stable. In conclusion, the present study showed that younger age at last birth and older age at menopause could increase the risk of BC.

Recent Progress of Organic Semiconductor Materials in Spintronics.

Spintronics, a new discipline focusing on the spin-dependent transport process of electrons, has been developing rapidly. Spin valves are the most significant carriers of spintronics utilizing the spin freedom of electrons. It is expected to pierce "Moore's Law" and become the core component in processors of the next generation. Organic semiconductors advance in their adjustable band gap, weak spin-orbit coupling and hyperfine interaction, excellent film-forming property, having enormous promise for spin valves. Here, the principle of spin valves is introduced, and the history and progress in organic spin injection and transport materials are summarized. Then we analyze the influence of spinterface on device performance and introduce reliable methods of constructing organic spin valves. Finally, the challenges for spin valves are discussed, and the future is proposed. We aim to draw the attention of researchers to organic spin valves and promote further research in spintronics through this paper.

An Efficient Blue-Emission Crystalline Thin-Film OLED Sensitized by "Hot Exciton" Fluorescent Dopant.

Crystalline thin-film organic light-emitting diodes (C-OLEDs) can achieve a large light emission and a low Joule-heat loss under low driving voltage due to the high carrier mobility of the crystalline thin films. However, it is urgent for the C-OLEDs to improve their external quantum efficiency (EQE). Here, a novel strategy is proposed using a doped "hot exciton" material to sensitize a high PLQY blue emitter in C-OLEDs. Benefiting from the capability of the "hot exciton" material harnessing triplet/singlet excitons, the C-OLED exhibits an efficiency breakthrough with a maximum EQE of 6.2%, a much enhanced blue photon output with pure blue emission Commission International de L'Eclairage (CIE) (0.14, 0.15), a low turn-on/operation voltage of 2.6 V(@1 cd m-2 )/3.8 V (@1000 cd m-2 ), and a maximum power efficiency (PE) of 9.4 lm W-1 . This work unlocks the potential of C-OLEDs for achieving high photon output with high EQE.

High-efficiency blue-emission crystalline organic light-emitting diodes sensitized by "hot exciton" fluorescent nanoaggregates.

Sensitizing fluorescent materials is an effective way to maximally use excitons and obtain high-efficiency blue organic light-emitting diodes (OLEDs). However, it is a persistent challenge for present amorphous thin-film OLEDs to improve photon emission under low driving voltage, severely impeding the development of OLED technology. Here, we propose a novel OLED architecture consisting of a crystalline host matrix (CHM) and embedded "hot exciton" nanoaggregates (HENAs), which effectively sensitize blue dopant (D) emission. Owing to the advantages of the crystalline thin-film route, the device exhibits largely enhanced blue photon output [Commission International de L'Eclairage coordinates of (0.15, 0.17)], with a low turn-on/operation voltage of 2.5 V (at 1 cd/m2)/3.3 V (at 1000 cd/m2), an extremely low Joule heat loss ratio (7.8% at 1000 cd/m2), and a maximum external quantum efficiency (EQE) up to 9.14%. These areal photon output features have outperformed the present amorphous thin-film blue OLEDs with high EQE, demonstrating that the CHM-HENA-D OLED is promising for future OLEDs.

Origin of Photovoltaics in Organic Solar Cells at Negligible Energy Level Offsets─An Insight of the Charge Accumulation Effect.

Reducing the energy level offset is one of the key elements of low open-circuit voltage loss in organic solar cells. However, the origin of charge separation driving force at negligible energy level offsets still remains unexplained. Herein, from the perspective of built-in potential caused by charge accumulation, we discuss the nonequilibrium energy level displacement as current passing with distinct variable current densities. Due to the different carrier mobilities of electrons and holes in organic semiconductor materials, carriers with high mobility will be rapidly transmitted to the electrode, while those with low mobility will remain in the materials, resulting in the accumulation of corresponding charges. It is suggested that the higher the carrier mobility, the better the efficiency of photovoltaic devices, with the balance of the charge transport.

A solution-processed n-type conducting polymer with ultrahigh conductivity.

Conducting polymers (CPs) with high conductivity and solution processability have made great advances since the pioneering work on doped polyacetylene1-3, thus creating the new field of 'organic synthetic metals,4. Various high-performance CPs have been realized, which enable the applications of several organic electronic devices5,6. Nevertheless, most CPs exhibit hole-dominant (p-type) transport behaviour7,8, whereas the development of n-type analogues lags far behind and only a few exhibit metallic state, typically limited by low doping efficiency and ambient instability. Here we present a facilely synthesized highly conductive n-type polymer poly(benzodifurandione) (PBFDO). The reaction combines oxidative polymerization and in situ reductive n-doping, greatly increasing the doping efficiency, and a doping level of almost 0.9 charges per repeating unit can be achieved. The resultant polymer exhibits a breakthrough conductivity of more than 2,000 S cm-1 with excellent stability and an unexpected solution processability without extra side chains or surfactants. Furthermore, detailed investigations on PBFDO show coherent charge-transport properties and existence of metallic state. The benchmark performances in electrochemical transistors and thermoelectric generators are further demonstrated, thus paving the way for application of the n-type CPs in organic electronics.

Stability of the Charged Nonfullerene Acceptors.

As an electric current passes through an organic semiconductor, a small number of organic molecules will inevitably act as a polaron state that is similar to an ionic charged state. The continuous device operation of organic semiconducting molecules is directly associated with the stability of the charged state. Herein, we choose the high-performance Y-series of nonfullerene acceptors to investigate the stability by a spectro-electrochemical technique. The results reveal the discoloration of molecules in the charged state and can be partially recovered after neutralization with about 10% irreversible part. It is found that the degree of the irreversible process is associated with halogen substituents at the end groups, and the irreversible reactions are also discussed. Our results reveal that the stability of a charged state can be improved by the fine-tuning of the molecular structures, and the local charge density can also be rapidly reduced by the high carrier mobility, the key factor to improving the stability of nonfullerene acceptors for better practical applications.

Comprehending radicals, diradicals and their bondings in aggregates of imide-fused polycyclic aromatic hydrocarbons.

Quantum effects such as ferromagnetism were regarded as rare in organic materials. When reduced to radical states, imide-fused polycyclic aromatic hydrocarbons (IPAHs) have shown room-temperature ferromagnetism in our recent work, to be a potential candidate as ferromagnetic semiconductor. Here, we use variational Davydov ansatz parametrized by density functional theory to investigate the structural and optical properties of IPAHs and their radicals at both molecule and aggregate levels. Our calculation reveals that hydrogen mainly gives rise to radicals and proves the formation of a mid-gap polaronic state, which is further evidenced by UV-vis absorption spectra simulations, in good agreement with experiments. The significant change of dispersion between the π-π stacking structure and planar structure implies the formation of radical-radical bonding (pancake bonding), which is revealed by simulations of NIR absorption signals and serves as the physical basis of long-range ferromagnetic orders. Absorption spectra of perylene diimide (PDI), terrylene diimide (TDI) and their radicals are also predicted.

lncRNA PSMB8-AS1 promotes colorectal cancer progression through sponging miR-1299 to upregulate ADAMTS5.

Long non-coding RNAs (lncRNAs) have been reported to be vital participants in tumor progression. Recently, lncRNA PSMB8-AS1 has been uncovered to facilitate pancreatic cancer progression by regulating miR-382-3p/STAT1/PD-L1 network. Nonetheless, the role of PSMB8-AS1 and its underlying mechanism have not been well-explored in colorectal cancer (CRC). The expression of RNAs or proteins was detected via qRT-PCR or western blot assays. Functional assays were involved in evaluating the effects of PSMB8-AS1/miR-1299/ADAMTS5 on the malignant behaviors of CRC cells. The molecular mechanism of PSMB8-AS1 was explored via mechanism analyses in CRC cells. Based on experimental results, PSMB8-AS1 expression was notably higher in CRC cell lines than in normal cells. The downregulation of PSMB8-AS1 repressed cell viability, proliferation, migration, invasion, and epithelial-mesenchymal transition (EMT) of CRC while promoting cell apoptosis. It was also revealed that PSMB8-AS1 could sponge miR-1299 to upregulate ADAMTS5 in CRC cells. In rescue assays, we further discovered that miR-1299 inhibition or ADAMTS5 overexpression abrogated the suppressive influence of PSMB8-AS1 deficiency on CRC cell growth. In addition, PSMB8-AS1 was validated to induce M2 polarization. In conclusion, PSMB8-AS1 sponges miR-1299 to increase PSMB8-AS1 expression, thus promoting CRC cell growth.

Electrocleavage Synthesis of Solution-Processed, Imine-Linked, and Crystalline Covalent Organic Framework Thin Films.

Developing a general, facile, and direct strategy for synthesizing thin films of covalent organic frameworks (COFs) is a major challenge in this field. Herein, we report an unprecedented electrocleavage synthesis strategy to produce imine-linked COF films directly on electrodes from electrolyte solutions at room temperature. This strategy enables the cathodic exfoliation of the COF powders to nanosheets by electrochemical reduction and protonation, followed by nanosheets migrating to the anode and reproducing the COF structures by anodic oxidation. Our method is adaptable with most imine-linked COFs by virtue of the low redox potential of the imine bonds, whereas the COF films possess high crystallinity and hierarchical porosity. We highlight these COF films as a superb platform for promoting mass transfer by demonstrating their extraordinarily rapid iodine adsorption with record-high rate constants.