Achieving Record External Quantum Efficiency of 11.5 % in Solution-Processable Deep-Blue Organic Light-Emitting Diodes Utilizing Hot Exciton Mechanism.

High performance solution-processable deep-blue emitters with a Commission International de l'Eclairage (CIE) coordinate of CIEy≤0.08 are highly desired in ultrahigh-definition display. Although, deep-blue materials with hybridized local and charge-transfer (HLCT) excited-state feature are promising candidates, their rigidity and planar molecular structures limit their application in solution-processing technique. Herein, four novel deep-blue solution-processable HLCT emitters were first proposed by attaching rigid imide aliphatic rings as functional units onto the HLCT emitting core. The functional units not only improve solubility, enhance thermal properties and morphological stability of the emitting core, but also promote photoluminescence efficiency, balance charge carrier transport, and inhibit aggregation-caused quenching effect due to the weak electron-withdrawing property as well as steric hindrance. The corresponding solution-processable organic light-emitting diodes (OLEDs) substantiate an unprecedented maximum external quantum efficiency (EQEmax) of 11.5 % with an emission peak at 456 nm and excellent colour purity (full width at half maximum=56 nm and CIEy=0.09). These efficiencies represent the state-of-the-art device performance among the solution-processable blue OLEDs based on the "hot exciton" mechanism. This simple strategy opens up a new avenue for designing highly efficient solution-processable deep-blue organic luminescent materials.

Engineering Diselenide-IR780 Homodimeric Nanoassemblies with Enhanced Photodynamic and Immunotherapeutic Effects for Triple-Negative Breast Cancer Treatment.

Photodynamic therapy (PDT) has emerged as an efficient approach for non-invasive cancer treatment. However, organic small-molecule photosensitizers are often associated with defects in hydrophobicity, poor photostability, and aggregation-caused quenching, which limit their application. Usually, the carrier-assisted drug delivery system is a common strategy to solve the above obstacles, but additional carrier material could increase the risk of potential biological toxicity. The carrier-free drug delivery system with easy preparation and high drug-loading capability is proposed subsequently as a potential strategy to develop the clinical use of hydrophobic drugs. Herein, we rationally designed three IR780-based carrier-free nanosystems formed by carbon/disulfide/diselenide bond conjugated IR780-based homodimers. The IR780-based homodimers could self-assemble to form nanoparticles (DC-NP, DS-NP, DSe-NP) and exhibited higher reactive oxygen species generation capability and photostability than free IR780, in which DSe-NP with 808 nm laser irradiation performed best and resulted in the strongest cytotoxicity to 4T1 cells. Meanwhile, the glutathione consumption ability of DSe-NP boosted its PDT effect and then induced excessive oxidative stress of 4T1 cells, increasing antitumor efficacy by enhancing immunogenic cell death further. In tumor-bearing mice, DSe-NP displayed obvious tumor site accumulation, which obviously inhibited tumor growth and metastasis, and enhanced the immunological effect by effectively inducing dendritic cells to mature and activating T lymphocytes and natural killer cells. In summary, our study presented an IR780-based carrier-free nanodelivery system for a combination of PDT and immunity therapy and established expanding the application of organic small-molecule photosensitizers by an approach of carrier-free drug delivery system.

Ultralow Coefficient of Thermal Expansion and a High Colorless Transparent Polyimide Film Realized Through a Reinforced Hydrogen-Bond Network by In Situ Polymerization of Aromatic Polyamide in Colorless Polyimide.

Colorless polyimides (CPIs) are a key substrate material for flexible organic light-emitting diode (OLED) displays and have attracted worldwide attention. Here, in this paper, the dispersion and interfacial interaction of aromatic polyamide (PA) in CPI (synthesized from 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) and 2,2'-bis(trifluoromethyl)benzidine (TFMB)) were significantly improved by in situ polymerization, and colorless transparent macromolecular polyimide composites (CPI-PAx) were successfully prepared by PA and CPI. By adjusting the ratio of PA to CPI, a high-performance engineering plastic with excellent film-forming properties was obtained. Molecular simulations confirmed the uniform distribution of PA in CPI and its interaction in polymers. In CPI-PAx, the CPI was locked by the PA chain, and numerous molecular chains were mutually entangled to form a hydrogen-bond network structure. Due to the strong interaction between the chains imparted by the hydrogen bonds of the PA, they do not slide under external forces and heating. In addition, the additive PA has excellent dimensional stability, thermal, and mechanical properties, and CPI has outstanding optical properties, so the synthesized CPI-PAx combines the comprehensive properties of PA and CPI. The CPI-PAx has excellent thermal and mechanical properties, with a thermal decomposition temperature of 499 °C, a glass transition temperature of 385 °C, a coefficient of thermal expansion of 0.8 ppm K-1, a tensile strength of 50.9 MPa, and an elastic modulus of 3.9 GPa. Particularly, CPI-PAx has a 90% transmittance in the visible region. These data prove that the strategy of combining PA and CPI by in situ polymerization is an effective method to circumvent the bottleneck of CPI in the current flexible window application, and this design strategy is universal.

Benzoxazole-Based Hybridized Local and Charge-Transfer Deep-Blue Emitters for Solution-Processable Organic Light-Emitting Diodes and the In fluences of Hexahydrophthalimido.

Hybridized local and charge-transfer (HLCT) emitters have attracted extensive attention, but the insolubility and severe self-aggregation tendency restrict their applications in solution-processable organic light-emitting diodes (OLEDs), particularly deep-blue OLEDs. Herein, two novel benzoxazole-based solution-processable HLCT emitters (BPCP and BPCPCHY) are designed and synthesized, in which benzoxazole acts as an acceptor, carbazole acts as a donor, and hexahydrophthalimido (HP, with a large intramolecular torsion angle and spatial distortion characteristics) acts as a bulky modified end-group with weak electron-withdrawing effects. Both BPCP and BPCPCHY exhibit HLCT characteristics and emit near ultraviolet in toluene at 404 and 399 nm. Compared to the BPCP, the BPCPCHY solid shows much better thermal stability (Tg, 187 vs 110 °C), higher oscillator strengths of the S1-to-S0 transition (0.5346 vs 0.4809), and faster kr (1.1 × 108 vs 7.5 × 107 s-1) and thus a much higher ΦPL in the neat film. The introduction of HP groups greatly suppresses the intra-/intermolecular charge-transfer effect and self-aggregation trends, and the BPCPCHY neat films placed in air for 3 months can still maintain an excellent amorphous morphology. The solution-processable deep-blue OLEDs utilizing BPCP and BPCPCHY achieved a CIEy of 0.06 with maximum external quantum efficiency (EQEmax) values of 7.19 and 8.53%, respectively, which are among the best results of the solution-processable deep-blue OLEDs based on the "hot exciton" mechanism. All of the above results indicate that benzoxazole is an excellent acceptor for constructing deep-blue HLCT materials, and the strategy of introducing HP as a modified end-group into an HLCT emitter provides a new perspective to develop solution-processable efficient deep-blue OLEDs with high morphological stability.

Temperature-Resistant Intrinsic High Dielectric Constant Polyimides: More Flexibility of the Dipoles, Larger Permittivity of the Materials.

High dielectric constant polymers have been widely studied and concerned in modern industry, and the induction of polar groups has been confirmed to be effective for high permittivity. However, the way of connection of polar groups with the polymer backbone and the mechanism of their effect on the dielectric properties are unclear and rarely reported. In this study, three polyimides (C0-SPI, C1-SPI, and C2-SPI) with the same rigid backbone and different linking groups to the dipoles were designed and synthesized. With their rigid structure, all of the polyimides show excellent thermal stability. With the increase in the flexibility of linking groups, the dielectric constant of C0-SPI, C1-SPI, and C2-SPI enhanced in turn, showing values of 5.6, 6.0, and 6.5 at 100 Hz, respectively. Further studies have shown that the flexibility of polar groups affected the dipole polarization, which was positively related to the dielectric constant. Based on their high permittivity and high temperature resistance, the polyimides exhibited outstanding energy storage capacity even at 200 °C. This discovery reveals the behavior of the dipoles in polymers, providing an effective strategy for the design of high dielectric constant materials.