Precise modulation of the active layer morphology to optimize exciton dissociation and charge collection efficiency is the research priority in organic solar cells (OSCs). In this work, two novel additives, TFFB as well as TCFB, are proposed and doped into acceptor using layer-by-layer deposition method to realize high-performance bilayer OSCs based on D18-Cl/Y6 system. The asymmetric additive TFFB was introduced to improve molecular polarity, facilitate molecular stacking and promote film crystallization. Compared to the control devices without additive-treated, power conversion efficiency (PCE) of D18-Cl/Y6(TFFB) OSCs was increased from 18.04% to 18.85%. Furthermore, TCFB with trichloromethyl instead of trifluoromethyl caused large quadrupole moment, which further enhanced the intermolecular interactions and induced the components distribution to form a better three-dimensional morphology structure. Corresponding D18-Cl/Y6(TCFB) devices achieved an excellent PCE of 19.15%, one of the highest PCE reported for binary OSCs to date. In addition, TCFB-treated devices exhibited favorable storage stability, remaining over 95% of the original efficiency after 2500 hours of placement. This study presents a simple and valid method that utilizing the role of quadrupole moment to optimize the hierarchical morphology and improve the charge dynamics process, finally realizing highly efficient and stable OSCs.

Strategic design of solid additives for regulating molecular aggregation and crystallinity in organic photovoltaic systems is crucial for enhancing device efficiency and stability. Herein, we introduce 3,5-dibromoanisole (DBA), a volatile solid additive synergistically integrating halogen and alkoxy functionalities, to optimize the PM6:Y6 active layer. DBA simultaneously interacts with both PM6 and Y6, promoting face-on molecular orientation and fibrillar network formation. Consequently, DBA-treated devices achieve a power conversion efficiency (PCE) of 18.34%, with a short-circuit current density (J_SC) of 28.24 mA·cm^–2 and a fill factor (FF) of 78.6%, surpassing the control device (PCE = 17.13%). Notably, the DBA additive exhibits exceptional stability and demonstrates broad applicability across multiple material systems. This study establishes a universal framework for designing multifunctional solid additives, paving the way for scalable, high-efficiency organic solar cells (OSCs).

Atherosclerosis (AS), a chronic vascular lesion, constitutes the primary pathological basis for a variety of cardiovascular diseases that account for 85% of total cardiovascular mortality. The accurate identification of AS is of critical significance for early clinical diagnosis and therapeutic interventions for associated diseases. Herein, we report a changeable π-conjugated probe (ASOCl-1) capable of specific AS imaging with resistance to serum protein interference and microenvironmental perturbations. ASOCl-1 itself was non-conjugated and non-fluorescent. Upon the activation by inflammatory biomarker hypochlorite (OCl⁻), the probe underwent a molecular rearrangement to generate a near-infrared fluorophore oxazine, with environmental-insusceptible response and anti-interference from serum protein. ASOCl-1 has been used to image OCl⁻ inside foam cells, a type of cell derived from macrophages at the AS sites. Most importantly, ASOCl-1 could achieve in vivo, ex vivo and slice imaging of AS mice. The satisfactory imaging performance and anti-interference capability of ASOCl-1 make it a potential tool for AS imaging diagnosis and disease progression monitoring.

Ultrasmall palladium nanoclusters have garnered significant attention due to their exceptional catalytic performance. However, their high surface energy always leads to aggregation, reducing the number of active sites and thereby decreasing catalytic efficiency. Herein, a molecular cage (RCC3) was utilized as a confined environment to stabilize ultrasmall PdNCs. The excellent solubility and open framework of cages not only enhance the solubility of palladium nanoclusters but also significantly improve their catalytic activity and stability. The prepared palladium nanoclusters were found to exhibit both peroxidase-like and oxidase-like activities. Under acidic conditions, the protonation of the molecular cage framework facilitates the assembly of ionic Pd nanoclusters with negatively charged enzymes through electrostatic interactions, forming a cascade system. The system is capable of detecting substrates, such as glucose and ascorbic acid, providing a highly catalytic platform for biosensing applications.

Catalytic dehydrogenative aromatization (CDA) has emerged as a powerful strategy for the synthesis of substituted phenols. However, most of the known CDA methods suffer from limited functional group compatibility due to the use of strong oxidants, reductants, or bases. Herein, we report a (cis-P₂Cl)Ir-catalyzed CDA reaction enabled by transfer dehydrogenation (TD). This catalytic system is effective for CDA of both cyclohexanone and cyclohexanol derivatives and demonstrates excellent tolerance toward a variety of functional groups, including readily oxidizable electron-rich heterocycles. DFT studies further reveal that the (cis-P₂Cl)Ir catalyst is thermodynamically disfavored for the formation of a potential out-of-cycle catalyst species, iridium phenoxyl hydride complex, via oxidative addition of the phenol O–H bond, thereby preventing catalyst inhibition observed in the previously reported TD system.

High valent iron complexes Fe-X have been known to transfer their X group toward carbon radical species to form R–X bond. To utilize this capability of iron catalyst, novel photo-induced iron catalysis system had been developed in the difunctionalization of alkenes in the presence of radical initiator. However, the details of the reaction mechanism are still unclear, especially the transformations of the photocatalyst and the iron catalyst during the catalytic turnover. Herein, we expanded the photo-driven non-heme iron complex catalyzed thiocyanation of styrene substrate. This protocol exhibited broad substrate scope and high efficiency. Detailed mechanistic studies using various spectroscopies, such as UV-vis, mass spectrometry, transient absorption spectroscopy and X-ray absorption spectroscopy, revealed the transformations of photocatalyst [Ir^III(ppy)₃] and group transfer catalyst [Fe^II(bpmen)]²⁺. Real-time spectroscopies combined with mechanistic experiments demonstrated that [Ir^IV(ppy)₃]⁺ and [Fe^III(bpmen)]³⁺ were the key intermediates involved in the reaction cycle.

Catalytic asymmetric hydrophosphination of unsaturated substrates has been proven to be one of the most straightforward ways to achieve chiral phosphine compounds. Although the methodologies of transition metals and organocatalysts catalyzed enantioselective hydrophosphination reactions have been well developed during the last decade, the enantioselective construction of quinoline and isoquinoline-based phosphines remains challenging. Furthermore, the chiral quinoline-based phosphines play a significant role in the preparation of chiral P,N-ligands. Herein, we report a comprehensive investigation for the asymmetric addition of diarylphosphine oxides to a wide range of α,β-unsaturated quinolines and isoquinolines, catalyzed by commercial chiral phosphoric acid, affording the corresponding products with up to 99% yield and 98% ee.

Inspired by natural Ca²⁺ channels, we design and synthesize a type of artificial Ca²⁺ carriers using o-phenanthroline-oxadiazole-based foldamers. Through the incorporation of negative charges into cavity-containing foldamers, highly selective calcium ion transmembrane transport can be achieved, leading to the identification of two highly efficient Ca²⁺ carriers. Systematic investigation revealed a positive correlation between the number of negative charges on the foldamers and the foldamers‘ cation-binding affinity. Furthermore, the size-selective effect, achieved through precise matching between the foldamer cavity dimensions and Ca²⁺ ion size, resulted in an unprecedented Ca²⁺/Mg²⁺ selectivity ratio (S_Ca/Mg), reaching record S_Ca/Mg values greater than 100–the highest of all artificial Ca²⁺ carriers reported to date. Moreover, artificial Ca²⁺ carriers show high Ca²⁺ transport activity (EC₅₀ = 190 nM). This simple and modular approach enables tailored design of divalent cation transporters, thus providing promising applications for artificial divalent cation transporters in the fields of biochemistry and material chemistry.

Reports on large-scale syntheses of rare deoxy sugars are notably limited, which poses a significant obstacle to the identification of glycans containing these rare sugars as potential therapeutic agents in the treatment of infectious diseases. In this manuscript, we present a hectogram-scale synthesis of the rare 3-amino sugar, saccharosamine, which is an essential component of the heptadecasaccharide saccharomicins, demonstrating considerable potential for the development of a novel class of antibiotics. The synthesis was initiated from the naturally abundant mannose and involved three batch processes in conjunction with five continuous flow processes, representing the most efficient synthetic pathway established to date. A total of five purification steps were conducted, and the process was meticulously designed to obviate the necessity for column chromatography. The effectiveness of these streamlined procedures, along with straightforward manipulation and purification protocols, effectively addresses the challenges associated with scaling up and provides a viable and environmentally sustainable solution for the rapid synthesis of related rare deoxy sugars.

Natural biomolecular structures possess an inherent ability to encode chiral conformations, thus the generation and regulation of chiroptical activity is crucial. While artificial polymers hold special significance in understanding life's origins, the fundamental connections between the racemic architecture and functional characteristics still need to be fully investigated. Herein, this study reports the generation and regulation of the global chirality and helical sense in racemic polymer systems, focusing on the synergistic effects of liquid crystallinity (LC) and solvophobic interaction. By systematically varying the length of alkyl spacers and the degree of polymerization (DP) of the core-forming azobenzene (Azo) blocks, the chiral communications, morphological transitions and chiroptical properties of the racemic nanoaggregates can be precisely controlled. Furthermore, the proposed “first come, first serve” (FF) and the “late-comer lives above” (LA) effect are broadly applicable and are expected to be applied to various types of racemic polymer systems. This work provides valuable insights into the design of self-assembled systems with tunable global chirality and morphology, thereby advancing the understanding of the origins of homochirality in nature.

The direct C(sp²)-H bond alkylation of maleimides using iminophosphorane-induced Fe(III)-catalyzed HAT (hydrogen atom transfer) strategy was achieved, and a series of novel alkyl maleimide derivatives were synthesized. The reaction has the characteristics of mild conditions, widespread functional group compatibility and substrates adaptability. The mechanism study shows that it mainly involves MHAT (metal-catalyzed hydrogen atom transfer), radical conjugate addition, SET (single electron transfer) processes, and theoretical calculations reveal that the critical step is that phosphorus radical intermediate G is converted to phosphorus cationic intermediate I. The research provides a new insight into the direct functionalization of C(sp²)-H to form C(sp²)-C(sp³) bonds via the HAT strategy.

1-Isoquinolin-1(2H)-one skeleton exists widely in natural products, pharmaceuticals and materials. We disclose here a fluorine effect and catalyst cooperatively induced regioselective or regiospecific 3,4-functionalization of unsymmetric 2-CF₃-1,3-enynes. The presence of trifluoromethyl group is determinable for the regioselectivity. When the CF₃ group was replaced with the methyl or amide group, the regioselectivity decreased to a ratio of 1.3 : 1 or 1 : 1.7, respectively. For alkyl substituted β-CF₃-1,3-enynes, a regiospecificity was obtained. This strategy features excellent regioselectivity, broad substrate scope and high functional group tolerance. Mechanistic studies showed that C–H bond activation is the rate-limiting step.

Moisture enabled electric generation (MEG) is an innovative green energy technology that converts the chemical potential energy of atmospheric water vapor into electricity. Here, we report a novel molecular-level zero-dimensional (0D) perovskite-based MEG device that efficiently harvests ambient moisture to generate electric power, which makes perovskite a new kind of potential MEG. The 0D perovskite, DAP₂PbI₆, (where DAP is 1,3-bis(ammonium)-2-hydroxypropane diiodide.) features a unique hydrogen-bonding network formed between its ammonium (–NH₃⁺) and hydroxyl (–OH) groups, imparting water stability and remarkable hydrophilicity. Such robust interactions facilitate water adsorption and the subsequent release of hydrogen ions under humid conditions. These protonic species establish an ion gradient, driving a directional current via the ion-gradient diffusion–induced voltage. We demonstrated a maximum volumetric power density of 45 mW·cm^–3—substantially exceeding previously reported values for protein- or carbon-based MEG. Additionally, SEM and AFM analyses confirm DAP₂PbI₆ is stable upon moisture exposure, while temperature-dependent impedance spectroscopy and theoretical calculations reveal that proton diffusion is the primary mechanism for the observed moisture-driven electricity. These findings underscore the promise of hydrophilic 0D perovskite materials for high-efficiency MEG and pave the way for next-generation sustainable power applications.

The stabilization of active molecules is significantly important for chemistry, especially for the bioactive molecules. In this work, we report the synthesis and characterization of three tetrahedral Fe₄L₆ cages, which are water-soluble and functionalized with or without PEG chains. All cages can physically trap NO molecules in their cavities to prevent a reaction with O₂. Single-crystal X-ray diffraction (SCXRD), Griess assay, electron paramagnetic resonance (EPR) spectroscopy, and fluorescence assay demonstrate that NO molecules were encapsulated and stabilized by these cage molecules through the formation of host-guest supramolecules. These NO-loaded cages show high antibacterial activities for inhibiting Staphylococcus aureus and Escherichia coli, providing a convenient method for making antibiotic agents. Moreover, these PEG-functionalized cages exhibit excellent biocompatibility, providing a new strategy for developing materials for NO delivery in biomedical applications

The remarkable biological activities of γ-aminobutyric acid derivatives (GABAs) spurred the exploration of green and efficient synthetic methods to construct these scaffolds. Herein, we have developed a catalyst-free photoinduced strategy for the redox-neutral three-component carboimination of alkenes, enabling efficient and modular assembly of a wide range of γ-aminobutyric acid derivatives. Mechanistic studies indicate that this reaction is initiated with an electron donor-acceptor complex between deprotonated malonates and O-aryl oximes. Furthermore, the resulting products could be further converted to functionalized γ-lactam derivatives through an acidic lactamization process.

The development of luminescent radicals with α-type transition properties is significant for advancing the understanding of luminescence mechanisms and photophysical properties in radical-based systems. Here, we present a straightforward strategy for acquiring stable luminescent radicals with α-type transition by directly decorating bis(2,4,6-trichlorophenyl)methyl radicals (BTM)-based luminescent radicals with strong electron acceptors. This approach effectively narrows the energy gap between the singly occupied molecular orbital (SOMOα) and lowest doubly unoccupied molecular orbital (LUMOα) (ΔE_{SOMOα→LOMOα}), enabling a transform of luminescent radicals from the conventional β-type transition to the rare α-type transition upon D₀→D₁ excitation process. The α-type transition was experimentally validated through the fabrication of organic light-emitting diodes (OLEDs) incorporating appropriate host materials. The result also expands the selection of available host materials for OLED devices exploiting radicals as emitters, as more host materials with higher highest occupied molecular orbital (HOMO) can now be considered. This work not only establishes a rational molecular design strategy for luminescent radicals with α-type transition but also provides valuable insights to guide future research in radical-based optoelectronic materials.

Organofluorine compounds have consistently played a pivotal role in chemical synthesis, materials development, and drug discovery. Among these, chiral organofluorine compounds have emerged as a significant focus of research. Gem-difluoroalkenes and difluoroenoxysilanes, owing to their high reactivity and modifiability, are extensively employed in the synthesis of chiral organofluorine compounds. This review summarizes recent research progress in the use of these molecules in asymmetric synthesis. Their application in synthesizing biologically active chiral molecules could open new possibilities and lead to unexpected breakthroughs in medicinal chemistry.

Over the past few decades, first-row transition metal complexes have emerged as promising candidates for photocatalyst design. By strategically selecting ligands and optimizing their structures and configurations, researchers have developed a range of photoactive complexes of copper, nickel, iron, cobalt, chromium, and manganese, which exhibit distinct photoactivity compared to conventional heavy metal complexes and organic dyes. Despite these advances, their application in organic synthesis remains in its early stages. This comprehensive review endeavors to trace the evolution of photoactive first-row transition metal complexes, with a particular focus on Cr, Mn, Co, and Fe systems as triplet-state photosensitizers and/or photoredox catalysts in organic transformations. Through a detailed analysis of design principles, reaction mechanisms, and synthetic utility, we highlight both the transformative potential and current limitations of these cost-effective, Earth-abundant metal complexes in photocatalysis.