Aggregation Enhanced Thermally Activated Delayed Fluorescence through Spin-Orbit Coupling Regulation.

Integrating aggregation-induced emission (AIE) into thermally activated delayed fluorescence (TADF) emitters holds great promise for the advancement of highly efficient organic light emitting diodes (OLEDs). Despite recent advancements, a thorough comprehension of the underlying mechanisms remains imperative for the practical application of such materials. In this work, we introduce a novel approach aimed at modulating the TADF process by manipulating dynamic processes in excited states through aggregation effect. Our findings reveal that aggregation not only enhances both prompt and delayed fluorescence simultaneously but also imposes constraints on molecular reorientation. This constraint reinforces spin-orbit coupling and reduces the energy gap between singlets and triplets. These insights deepen our understanding of the fundamental mechanisms governing the aggregation effect on TADF materials and provide valuable guidance for the design of high-efficiency photoluminescent materials.

SNHG15-mediated feedback loop interplays with HNRNPA1/SLC7A11/GPX4 pathway to promote gastric cancer progression.

Dysregulation of long noncoding RNA (lncRNA) expression plays a pivotal role in the initiation and progression of gastric cancer (GC). However, the regulation of lncRNA SNHG15 in GC has not been well studied. Mechanisms for ferroptosis by SNHG15 have not been revealed. Here, we aimed to explore SNHG15-mediated biological functions and underlying molecular mechanisms in GC. The novel SNHG15 was identified by analyzing RNA-sequencing (RNA-seq) data of GC tissues from our cohort and TCGA dataset, and further validated by qRT-PCR in GC cells and tissues. Gain- and loss-of-function assays were performed to examine the role of SNHG15 on GC both in vitro and in vivo. SNHG15 was highly expressed in GC. The enhanced SNHG15 was positively correlated with malignant stage and poor prognosis in GC patients. Gain- and loss-of-function studies showed that SNHG15 was required to affect GC cell growth, migration and invasion both in vitro and in vivo. Mechanistically, the oncogenic transcription factors E2F1 and MYC could bind to the SNHG15 promoter and enhance its expression. Meanwhile, SNHG15 increased E2F1 and MYC mRNA expression by sponging miR-24-3p. Notably, SNHG15 could also enhance the stability of SLC7A11 in the cytoplasm by competitively binding HNRNPA1. In addition, SNHG15 inhibited ferroptosis through an HNRNPA1-dependent regulation of SLC7A11/GPX4 axis. Our results support a novel model in which E2F1- and MYC-activated SNHG15 regulates ferroptosis via an HNRNPA1-dependent modulation of the SLC7A11/GPX4 axis, which serves as the critical effectors in GC progression, and provides a new therapeutic direction in the treatment of GC.

Predictors of iatrogenic splenic injury in radical gastrectomy for gastric cancer.

Background: Iatrogenic splenic injury (ISI) is a recognized complication in radical gastrectomy that may result in incidental splenectomy (IS). However, the predictors of such events remain largely unknown. Methods: Medical records of the patients who underwent radical gastrectomy at our institution between January 2015 and December 2022 were retrospectively reviewed. Potential predictors of ISI and IS were collected and analyzed by multivariate logistic regression. Results were reported as an odds ratio (OR) with 95% confidence intervals (CI). Results: A total of 2916 patients were included, of whom 211 patients (7.2%) suffered from ISI and 75 patients (2.6%) underwent IS. Multivariate analysis demonstrated that BMI≥25 (OR: 3.198 (2.356-4.326), p<0.001), total gastrectomy (OR: 2.201 (1.601-3.025), p<0.001), and the existence of "criminal fold" (OR: 13.899 (2.824-251.597), p=0.011) were independent predictive risk factors for ISI; whereas laparoscopic surgical approach (OR: 0.048 (0.007-0.172), p<0.001) was a protective factor for ISI. Moreover, the existence of "criminal fold" (OR: 15.745 (3.106-288.470), p=0.008) and BMI≥25 (OR: 2.498 (1.002-6.046), p=0.044) were identified as independent risk factors of ISI under laparoscopic gastrectomy. There was no association between sex, age, previous abdominal surgery, neoadjuvant therapy, outlet obstruction, tumor stage, nodal stage, and total lymph node retrieved and ISI. Conclusions: BMI≥25 and total gastrectomy can predict high risk of ISI during radical gastrectomy. Laparoscopic surgery is superior to open gastrectomy in lowing the risk of ISI.

Heavy-Atom Effect Regulating Room-Temperature Phosphorescence of Organic-Inorganic Zn-Based Halides for White-Light Emission.

Organic-inorganic metal halides (OIMHs) with room-temperature phosphorescence (RTP) properties have aroused great research enthusiasm as outstanding broadband white-light emitters. Current studies on OIMHs with white-light emission were achieved via self-trapped excitons (STEs), but the unclear mechanism of STE formation is not favorable for the design of materials. In this work, zero-dimensional OIMHs composed of organic 3,4,5-trimethoxybenzylamine (TBA) and zine halide were synthesized, which enhanced the ratio of the RTP emission to the fluorescence emission from the TBA ligand. The experimental and mechanistic analyses demonstrate that the manageable RTP is mainly caused by the heavy-atom effect. In particular, by adjusting the incorporation ratio of halogen, an obvious white-light emission with a chromaticity coordinate value of (0.31, 0.33) can be achieved. This work developed a method for regulating the RTP of OIMHs with the heavy-atom effect to realize white-light emission, providing a new idea for the design of white-light emission materials.

Shape-Dependent Optical Waveguides and Low-Threshold Lasers from Polymorphic Two-Dimensional Organic Single Crystals.

Organic single crystals (OSCs) with uniform morphologies and highly ordered molecular aggregations are promising for high-performance optoelectronic devices, such as organic solid-state lasers (OSSLs), organic light-emitting transistors (OLETs), and organic light-emitting diodes (OLEDs). However, manipulating OSC morphologies and aggregation is challenging. In this study, we synthesized two-dimensional (2D) OSCs of 4,4'-bis[(N-carbazole)styryl]biphenyl (BSBCz) in hexagonal and parallelogram microplate (H-MP and P-MP) forms. Both types exhibit H-aggregation in the 2D plate plane but with different molecular transition dipole moment (TDM) orientations. This leads to different photon coupling modes with H-MP and P-MP microcavities. H-MPs enable isotropic 2D-waveguiding, forming whispering gallery mode (WGM) resonators, while P-MPs create unidirectional waveguiding, forming Fabry-Pérot mode (FP) resonators. These resonators can generate low-threshold laser emissions at 467 and 473 nm, respectively, and exhibit superior lasing stability with a half-life exceeding 2 h. Our BSBCz microplate OSCs are attractive candidates to combine controlled organic microcavities with photon transporting for realizing future integrated optoelectronic devices.

Dual-Stimuli-Responsive Modulation Organic Afterglow Based on N─H Proton Migration Mechanism.

Organic afterglow materials have significant applications in information security and flexible electronic devices with unique optical properties. It is vital but challenging to develop organic afterglow materials possessing controlled output with multi-stimuli-responsive capacity. Herein, dimethyl terephthalate (DTT) is introduced as a strong proton acceptor. The migration direction of N─H protons on two compounds Hs can be regulated by altering the excitation wavelength (Ex) or amine stimulation, thereby achieving dual-stimuli-responsive afterglow emission. When the Ex is below 300 nm, protons migrate to S1-2 DTT , where strong interactions induce phosphorescent emission of Hs, resulting in afterglow behavior. Conversely, when the Ex is above 300 nm, protons interact with the S0 DTT weakly and the afterglow disappears. In view of amine-based compounds with higher proton accepting capabilities, it can snatch proton from S1-2 DTT and redirect the proton flow toward amine, effectively suppressing the afterglow but obtaining a new redshifted fluorescence emission with Δλ over 200 nm due to the high polarity of amine. Moreover, it is successfully demonstrated that the applications of dual-stimuli-responsive organic afterglow materials in information encryption based on the systematic excitation-wavelength-dependent (Ex-De) behavior and amine selectivity detection.

Switching from Thermally Activated Delayed Fluorescence in Single Crystals for Low-Threshold Laser to Room-temperature Phosphorescence in Amorphous-Film for Highly Efficient OLEDs.

Metal-organic phosphorescent complexes containing Ir or Pt are work horse in organic light-emitting diode (OLED) technology, which can harvest both singlet and triplet excitons in electroluminescence (EL) owing to strong heavy-atom effect. Recently, organic room-temperature phosphorescence (ORTP) have achieved high photoluminescence quantum yield (PLQY) in rigid crystalline state, which, however, is unsuitable for OLED fabrication, therefore leading to an EL efficiency far low behind those of metal-organic phosphorescent complexes. Here, we reported a luminescence mechanism switch from thermally activated delayed fluorescence (TADF) in single crystal microwires to ORTP in amorphous thin-films, based on a tert-butylcarbazole difluoroboron ß-diketonate derivative of DtCzBF2. Tightly packed and well-faceted single-crystal microwires exhibit aggregation induced emission (AIE), enabling TADF microlasers at 473 nm with an optical gain coefficient as high as 852 cm-1 . In contrast, loosely packed dimers of DtCzBF2 formed in guest-host amorphous thin-films decrease the oscillator strength of fluorescence transition but stabilize triplets for ORTP with a PLQY up to 61 %, leading to solution-processed OLEDs with EQE approaching 20 %. This study opens possibilities of low-cost ORTP emitters for high performance OLEDs and future low-threshold electrically injected organic semiconductor lasers (OSLs).

Photochemical Reaction Enabling the Engineering of Photonic Spin-Orbit Coupling in Organic-Crystal Optical Microcavities.

The control and active manipulation of spin-orbit coupling (SOC) in photonic systems are fundamental in the development of modern spin optics and topological photonic devices. Here, we demonstrate the control of an artificial Rashba-Dresselhaus (RD) SOC mediated by photochemical reactions in a microcavity filled with an organic single crystal of photochromic phase-change character. Splitting of the circular polarization components of the optical modes induced by photonic RD SOC is observed experimentally in momentum space. By applying an ultraviolet light beam, we control the spatial molecular orientation through a photochemical reaction, and with that we control the energies of the photonic modes. This way, we realize a reversible conversion of spin splitting of the optical modes with different energies, leading to an optically controlled switching between circularly and linearly polarized optical modes in our device. Our strategy of in situ and reversible engineering of SOC induced by a light field provides a promising approach to actively design and manipulate synthetic gauge fields toward future on-chip integration in photonics and topological photonic devices.

Space-Isolated Chromophore for Organic Blue Phosphorescence with High Efficiency and a Deep-Blue Lasing Characteristic.

High-efficiency blue phosphorescence and deep-blue laser emissions play a crucial role in organic optoelectronic applications. However, designing metal-free organic blue luminescence with high energy levels of excited states and suppression of nonradiative transitions remains a formidable challenge. Herein, we demonstrate a synthetic strategy for achieving a deep-blue laser and efficient phosphorescence based on confining chromophores in the tetrahedral structure of sp3 hybridization. The data analysis reveals that the construction of the quaternary carbon center contributes to spatially separated donors and acceptors and considerable steric constraints, prompting an effective intersystem crossing (ISC) process and suppressing nonradiative transitions. The negligible interaction between chromophores simultaneously produces a deep-blue fluorescent laser and blue phosphorescence with an efficiency up to 82.3%. This work opens the door to multifunctional blue-emitting materials with high efficiency, providing a high-potential candidate for electrically pumped organic lasers and energy efficient light-emitting diodes.

Elimination of Chirality in Three-Dimensionally Confined Open-Access Microcavities.

The emergent optical activity (OA) caused by anisotropic light emitter in microcavities is an important physical mechanism discovered recently, which leads to Rashba-Dresselhaus photonic spin-orbit (SO) coupling. In this study, we report a sharp contrast of the roles of the emergent OA in free and confined cavity photons, by observing the optical chirality in a planar-planar microcavity and its elimination in a concave-planar microcavity, evidenced by polarization-resolved white-light spectroscopy, which agrees well with the theoretical predictions based on the degenerate perturbation theory. Moreover, we theoretically predict that a slight phase gradient in real space can partially restore the effect of the emergent OA in confined cavity photons. The results are significant additions to the field of cavity spinoptronics and provide a novel method for manipulating photonic SO coupling in confined optical systems.

Host Surface-Induced Excitation Wavelength-Dependent Organic Afterglow.

The design and construction of organic afterglow materials is an attractive but formidably challenging task due to the low intersystem crossing efficiency and nonradiative decay. Here, we developed a host surface-induced strategy to achieve excitation wavelength-dependent (Ex-De) afterglow emission through a facile dropping process. The prepared PCz@dimethyl terephthalate (DTT)@paper system exhibits a room-temperature phosphorescence afterglow, with the lifetime up to 1077.1 ± 15 ms and duration time exceeding 6 s under ambient conditions. Furthermore, we can switch the afterglow emission on and off by adjusting the excitation wavelength below or above 300 nm, showing a remarkable Ex-De behavior. Spectral analysis demonstrated that the afterglow originates from the phosphorescence of PCz@DTT assemblies. The stepwise preparation process and detailed experiments (XRD, 1H NMR, and FT-IR analysis) proved the presence of strong intermolecular interactions between the carbonyl groups on the surface of DTT and the entire frame of PCz, which can inhibit the nonradiative processes of PCz to achieve afterglow emission. Theoretical calculations further manifested that DTT geometry alteration under different excitation beams is the main reason for the Ex-De afterglow. This work discloses an effective strategy for constructing smart Ex-De afterglow systems that can be fully exploited in a range of fields.

Dynamic Evolving Exothermicity Steers Ultrafast Formation of a Correlated Triplet Pair State.

Singlet fission (SF) presents an attractive solution to overcome the Shockley-Queisser limit of single-junction solar cells. The conversion from an initial singlet state to final triplet is mediated by the correlated triplet pair state 1(T1T1). Despite significant advancement on 1(T1T1) properties and its role in SF, a comprehensive understanding of the energetic landscape during SF is still unclear. Here, we study an unconventional SF system with excited-state aromaticity, i.e., cyano-substituted dipyrrolonaphtheridinedione derivative (DPND-CN), using time-resolved spectroscopy as a function of the temperature. We demonstrate that the population transfer from S1 to 1(T1T1) is driven by a time-dependent exothermicity resulting from the coherent coupling between electronic and spin degrees of freedom. This is followed by thermal-activated dissociation of 1(T1T1) to yield free triplets. Our results provide some new insight into the SF mechanism, which may guide the development of new efficient and stable SF materials for practical applications.

High-Performance Ambipolar and n-Type Emissive Semiconductors Based on Perfluorophenyl-Substituted Perylene and Anthracene.

Emissive organic semiconductors are highly demanding for organic light-emitting transistors (OLETs) and electrically pumped organic lasers (EPOLs). However, it remains a great challenge to obtain organic semiconductors with high carrier mobility and high photoluminescence quantum yield simultaneously. Here, a new design strategy is reported for highly emissive ambipolar and even n-type semiconductors by introducing perfluorophenyl groups into polycyclic aromatic hydrocarbons such as perylene and anthracene. The results reveal that 3,9-diperfluorophenyl perylene (5FDPP) exhibits the ambipolar semiconducting property with hole and electron mobilities up to 0.12 and 1.89 cm2 V-1 s-1 , and a photoluminescence quantum yield of 55%. One of the crystal forms of 5FDPA exhibits blue emission with an emission quantum yield of 52% and simultaneously shows the n-type semiconducting property with an electron mobility up to 2.65 cm2 V-1 s-1 , which is the highest value among the reported organic emissive n-type semiconductors. Furthermore, crystals of 5FDPP are utilized to fabricate OLETs by using Ag as source-drain electrodes. The electroluminescence is detected in the transporting channels with an external quantum efficiency (EQE) of up to 2.2%, and the current density is up to 145 kA cm-2 , which are among the highest values for single-component OLETs with symmetric electrodes.

Thermally Activated Long Persistent Luminescence of Organic Inorganic Metal Halides.

Long persistent luminescence (LPL) materials of SrAl2 O4 doped with Eu2+ or Dy3+ can maintain emission over hours after ceasing the excitation but suffer from insolubility, high cost, and harsh preparation. Recently, organic LPL of guest-host exciplex systems has been demonstrated via an intermediate charge-separated state with flexible design but poor air-stability. Here, we synthesized a nontoxic two-dimensional organic-inorganic metal hybrid halides (OIMHs), called PBA2 [ZnX4 ] with X=Br or Cl and PBA=4-phenylbenzylamine. These materials exhibit stable LPL emission over minutes at room-temperature, which is two orders of magnitude longer than those of previously reported OIMHs. The mechanism study shows that the LPL emission comes from thermally activated charge separation state rather than room-temperature phosphorescence. Moreover, the LPL of PBA2 [ZnX4 ] can be excited by low power sources, representing an effective strategy for developing low-cost and high-stability LPL systems.

Room-Temperature Electrical Field-Enhanced Ultrafast Switch in Organic Microcavity Polariton Condensates.

Integrated electro-optical switches are essential as one of the fundamental elements in the development of modern optoelectronics. As an architecture for photonic systems exciton polaritons, hybrid bosonic quasiparticles that possess unique properties derived from both excitons and photons, have shown much promise. For this system, we demonstrate a significant improvement of emitted intensity and condensation threshold by applying an electric field to a microcavity filled with an organic microbelt. Our theoretical investigations indicate that the electric field makes the excitons dipolar and induces an enhancement of the exciton-polariton interaction and of the polariton lifetime. Based on these electric field-induced changes, a sub-nanosecond electrical field-enhanced polariton condensate switch is realized at room temperature, providing the basis for developing an on-chip integrated photonic device in the strong light-matter coupling regime.

Circularly polarized electroluminescence from a single-crystal organic microcavity light-emitting diode based on photonic spin-orbit interactions.

Circularly polarized (CP) electroluminescence from organic light-emitting diodes (OLEDs) has aroused considerable attention for their potential in future display and photonic technologies. The development of CP-OLEDs relies largely on chiral-emitters, which not only remain rare owing to difficulties in design and synthesis but also limit the performance of electroluminescence. When the polarization (pseudospin) degrees of freedom of a photon interact with its orbital angular momentum, photonic spin-orbit interaction (SOI) emerges such as Rashba-Dresselhaus (RD) effect. Here, we demonstrate a chiral-emitter-free microcavity CP-OLED with a high dissymmetry factor (gEL) and high luminance by embedding a thin two-dimensional organic single crystal (2D-OSC) between two silver layers which serve as two metallic mirrors forming a microcavity and meanwhile also as two electrodes in an OLED architecture. In the presence of the RD effect, the SOIs in the birefringent 2D-OSC microcavity result in a controllable spin-splitting with CP dispersions. Thanks to the high emission efficiency and high carrier mobility of the OSC, chiral-emitter-free CP-OLEDs have been demonstrated exhibiting a high gEL of 1.1 and a maximum luminance of about 60000 cd/m2, which places our device among the best performing CP-OLEDs. This strategy opens an avenue for practical applications towards on-chip microcavity CP-OLEDs.

Circularly Polarized Lasing from a Microcavity Filled with Achiral Single-Crystalline Microribbons.

Organic circularly polarized (CP) lasers have received increasing attention due to their future photoelectric applications. Here, we demonstrate a CP laser from a pure organic crystal-filled microcavity without any chiral molecules or chiral structures. Benefited from the giant anisotropy and excellent laser gain of organic crystals, optical Rashba-Dresselhaus spin-orbit coupling effect can be induced and is conductive to the CP laser in such microcavities. The maximum dissymmetry factor of the CP lasing with opposite helicities reachs 1.2. Our strategy may provide a new idea for the design of CP lasers towards future 3D laser displays, information storage and other fields.

Compact-Type Quasi-2D Perovskite Based on Two Conventional 3D Perovskites.

Quasi-2D perovskites are natural quantum well (QW) structures composed of insulating organic layers inserted between conducting [An-1PbnX3n+1]2- slabs. The presence of the bulky organic layer improves the stability but meanwhile sacrifices carrier transport performance. By utilizing two A-site cations of formamidinium (FA+) and cesium (Cs+), we synthesize unique compact-type quasi-2D perovskites CsPbBr3@FABr. Instead of the bulky organic cations, the FA+ cation was employed to work as interlayer "spacer", while the smaller Cs+ cation was chosen to occupy perovskite cages. Transient absorption reveals an energy transfer from small-n-value QWs to large-n-value QWs, enabling a photoluminescence quantum yield (PLQY) of 36.1%. After further promoting the formation of middle-n-value QWs, the homogeneous QW distribution provides a complete energy cascade to access more efficient energy transfer, leading to significant PLQY raise to 70.1%. We break the shackles to report the first case of compact-type quasi-2D perovskites, providing new guidelines for designing high-performance perovskite materials for optoelectronic devices.

Robust singlet fission process in strong absorption π-expanded diketopyrrolopyrroles.

Singlet fission (SF) has drawn tremendous attention as a multiexciton generation process that could mitigate the thermal loss and boost the efficiency of solar energy conversion. Although a SF-based solar cell with an EQE above 100% has already been fabricated successfully, the practical efficiency of the corresponding devices is plagued by the limited scope of SF materials. Therefore, it is of great importance to design and develop new SF-capable compounds aiming at practical device application. In the current contribution, via a π-expanded strategy, we presented a new series of robust SF chromophores based on polycyclic DPP derivatives, Ex-DPPs. Compared to conventional DPP molecules, Ex-DPPs feature strong absorption with a fivefold extinction coefficient, good molecular rigidity to effectively restrain non-radiative deactivation, and an expanded π-skeleton which endow them with well-suited intermolecular packing geometries for achieving efficient SF process. These results not only provide a new type of high-efficiency SF chromophore but also address some basic guidelines for the design of potential SF materials targeting practical light harvesting applications.

Organic Phosphorescence Lasing Based on a Thermally Activated Delayed Fluorescence Emitter.

Organic phosphorescence materials provide an opportunity to use triplets for lasing. However, population inversion based on phosphorescence is hard to establish, owing to low luminescent quantum efficiency and intensive optical loss. By comparison, thermally activated delayed fluorescence emitters exhibit excellent optical gain with the aid of the reverse intersystem crossing (RISC) process. In this work, we designed a multifunctional gain material, not only serving as a thermally activated delayed fluorescence (TADF) emitter with excellent optical gain but also working as a phosphorescence source with high utilization of triplets. The lone pair of electrons in oxygen substitutions promotes a fast spin-flip and high delayed fluorescence quantum yield (ΦDF = 55%), enabling TADF amplified spontaneous emissions (ASE) of CH2Cl2 solution. Single-crystalline nanowires of H-aggregates effectively lower triplet energy levels with high phosphorescence quantum yield (ΦP = 27%), demonstrating Fabry-Perot mode phosphorescence lasing at 630 nm.