We describe a synergetic photoredox and CO 2 •− catalysis for a regioselective hydroarylation of 1-alkenyl carbonyls with cyano(hetero)aromatics via radical anion sorting. Using the carbon dioxide radical anion (CO 2 •−) as a powerful single electron reductant cooperated with the photoreductive catalysis, this protocol enables the simultaneous formation of dual radical anions through single electron reduction of alkenes and cyano(hetero)aromatics, respectively, followed by radical anion-radical anion coupling to achieve hydroarylation leading to β-(hetero)aryl alkyl carbonyl compounds in a highly regioselective manner. This hydroarylation reaction proceeds under mild conditions, exhibits broad functional-group compatibility and accommodates a wide range of alkenes and cyano(hetero)aromatics with exquisite regioselectivity.

To fully elucidate the function of trifluoromethoxy group in drug discovery and materials science, the efficient preparation of stereodefined analogues is essential. The established dehydroxytrifluoromethoxylation reaction, while synthetically useful, follows an S N1 mechanism and consequently produces racemic products. Herein, we report a stereospecific S N2 dehydroxytrifluoromethoxylation reaction. This protocol employs readily available 2,4-dinitro(trifluoromethoxy)benzene (DNTFB) as a trifluoromethoxide source and fluoro- N,N,N’,N’-tetramethylformamidinium hexafluorophosphate (TFFH) as a dual activator. TFFH activates the alcohol for isouronium formation and provides fluoride to liberate the CF 3O - anion from DNTFB. This stereospecific method offers a highly efficient, low-cost, and broadly applicable strategy for the late-stage modification of complex drug molecules.

The morphology of the active layer plays a crucial role in the performance of organic photovoltaics. Although volatile additives are commonly used to manipulate the morphology, their mechanism of action remain poorly understood. In this study, we conducted a systematic exploration of the mechanism of the traditional volatile additive 1-CN in film formation kinetics of typical PM6:Y6 system. We found that 1-CN induces a secondary aggregation effect, improving film morphology and promoting face-on crystalline orientation. Through elucidating its impact on exciton dynamics, we established a link between morphology optimization and increased exciton diffusion length and accelerated charge separation. Our findings unveil the unique mechanism of action of volatile additive, providing a new perspective for improving the morphology and enhancing the performance of organic photovoltaic devices.

Inverted (p-i-n) perovskite solar cells (PSCs) are favored by researchers owing to their superior compatibility with flexible substrates and tandem device fabrication. Additionally, the hole transport layer (HTL) serves as a template for perovskite growth, which is critical for enhancing the device performance. However, the current research on how the HTL promotes perovskite crystallization is insufficient. Here, 4PADCB, a self-assembled monolayer (SAM) hole transport material, was optimized as a superior template for perovskite growth through comparative analysis; accordingly, compact perovskite film with vertical growth was prepared. The better matched energy level alignment between 4PADCB and perovskite suppressed nonradiative recombination at the interface and enabled rapid hole extraction. Moreover, high-quality perovskite film growth on 4PADCB exhibited lower Young’s modulus and less residual stress. By integrating 4PADCB into p-i-n PSCs, the optimal device achieved a power conversion efficiency of 24.80%, with an open-circuit voltage of 1.156 V, thus achieving the best rank among devices without perovskite post-treatment, additives, dopants, or intermediate layers. Furthermore, the unencapsulated device demonstrated exceptional thermostability and photostability under maximum power point tracking. Thus, this work provides a new understanding for the development of novel SAMs and perovskite growth, and it is expected to further improve device performance.

Facile mass transport channel and accessible active sites is crucial for binder-free air electrode catalysts in rechargeable flexible zinc-air battery (ZAB). Herein, a ZnS/NH3 dual-assisted pyrolysis strategy is proposed to prepare N/S-doped hierarchical porous bamboo carbon cloth (HP-NS-BCC) as binder-free air electrode catalyst for ZAB. BCC fabric with abundant micropores is firstly used as flexible carbon support to facilitate the heteroatom-doping and construct the hierarchical porous structure. ZnS nanospheres and NH3 activization together facilitate the electronic modulation of carbon matrix by N/S-doping and optimize the macro/meso/micropores structure of carbon fibers. Benefiting from the highly-exposed N/S-induced sites with enhanced intrinsic activity, the optimized mass transport of biocarbon fibers, as well as the ultra-large specific surface area of 2436.1 m2 g-1, the resultant HP-NS-BCC catalyst exhibits improved kinetics for oxygen reduction/evolution reaction. When applied to rechargeable aqueous ZABs, it achieves a high open-circuit voltage of 1.516 V and a significant peak power density of 249.1 mW cm−2. As binder-free air electrode catalyst, the flexible ZAB also displays stable cycling over 500 cycles with a minimal voltage gap of 0.42 V, showcasing promising applications in flexible electronic devices.

A highly enantioselective palladium-catalyzed intramolecular Heck reaction of unactivated alkenes is developed, which provides a powerful route to access a broad range of chiral 3,3-disubstituted-2,3-dihydrobenzofurans bearing all-carbon quaternary stereocenter of interest in pharmaceutical research. Its salient features include high yield, excellent chemo- and enantioselectivity, mild condi-tions, a broad substrate scope as well as versatile transformations of the product.

A visible-light-induced photoredox-catalyzed regioselective and stereoselective C(sp2)-H amination of enamides with bench-stable and easily accessible N-aminopyridium salts is developed, affording synthetically and biologically prominent vicinal 1,2-diamine scaffolds in broad substrate scope and excellent functional group compatibility. The transformation proceeded through a radical pathway involving the Giese addition of the relatively electrophilic N-centered amidyl radical species to nucleophilic β-olefinic position of enamides followed by the ensuing single electron oxidation and β-H elimination, delivering geometrically-defined Z-configured β-amino enamides. The operational simplicity, environmentally friendliness and cost efficiency of this methodology has paved a new avenue to enrich the arsenal of synthetically crucial functionalized enamides and their derivatives.

Room-temperature sodium-sulfur (RT-Na/S) batteries display attractive potential in large-scale energy-storage, but their practical application was still restricted by the serious dissolution of polysulfides. Herein, supported by the constructing of interface engineering, the metal sulfide-carbon nanocomposite can be prepared with considerable electrochemical properties. Utilizing the double-helix structure of carrageenan-metal hydrogels as precursors, in-situ metal sulfide (MxSy) nanostructure/3D carbon aerogels (3D CAs) can be successfully constructed. Importantly, with the assistance of the vulcanization process, 3D carbon architecture was maintained in the composites and act as a skeleton to optimize their structural stability. As the anode of RT-Na/S batteries, ZnS/S@C and NiS2/S@C delivered an excellent cycling stability and rate performance (179.8mAhg−1 at 20Ag−1 after 10000 cycling for ZnS/S@C, 220.3 mAhg−1 at 10Ag−1 after 3000 cycling for NiS2/S@C). The detailed investigation of mechanism revealed that the powerful adsorption for Na2S4 was originated from 3D metal sulfide-carbon structure. The well-designed architecture of sulfide-carbon composites servers as an electrocatalyst to alleviate the shuttle effect of polysulfides, resulting in the long-term electrochemical stability. Given this, the work is expected to provide promising insights for designing advanced anode materials for RT-Na/S batteries.

Ten novel isocoumarins, including four pairs of enantiomers, were isolated from Artemisia dubia var. subdigitata (Asteraceae). Com-pounds 1, 2 and 3a/3b possessed a unique 6/6/6-tricyclic system comprising an unusual 1-(2-methylcyclohexyl) propan-1-one moiety fused with isocoumarin core skeleton. Compounds 4a/4b were characterized as an unexpected 2,5-dimethylcyclohexan-1-one scaffold, and compounds 5a/5b and 6a/6b were rare 1,2-seco-isocoumarin. Their structures and absolute configurations were elucidated through spectroscopic data, X-ray crystallography, ECD and NMR calculations with DP4+ analyses. Plausible biosynthetic pathways were proposed from the naturally occurring isocoumarin. Network pharmacological analysis suggested that the targets of compound 1 were significantly enriched in the cell cycle and PI3K-Akt signaling pathway. The molecular docking revealed that compound 1 had high binding affinity with CDK2 (total score: 6.8717). Furthermore, compounds 1 and 2 exhibited inhibitory activity on three human hepa-toma cell lines, with inhibitory ratios of 85.1% and 84.5% (HepG2), 88.2% and 87.3% (Huh7), and 69.2% and 69.1% (SK-Hep-1) at 200 μM, respectively.

The precise syntheses of transition–rare-earth metal clusters with desired structures remain a great challenge. Herein, by utilizing SO4 2– anion released by in-situ decomposition of sodium dodecyl sulfate (SDS) as a template, a series of novel high-nuclear ity 3d-4f clusters, formulated as [Ni24Pr22(μ3-OH)31(pida)24(SO4)4 (NO3)9(CH3 COO)3]·Br4·(NO3)11· 16H 2O·25CH3OH (1, H2pida = N-phenyliminodiacetic acid), [Ni24Nd22(μ3-OH)31(pida)24(SO4)4(NO3)9(CH3COO)3 ]·Br4·(NO3)11·14H2O· 24CH3OH·(2)·and [Ni24Gd22 (μ3-OH)36(bida)24(SO4)7(NO3)3(CH3 COO) 3]·(SO4)·Br4 ·(NO3)4·31H2O 32CH3OH (3, H 2 bida = N-benzyliminodiacetic acid), have been successfully isolated. X-ray crystal structure analyses reveal that all the cationic {Ni24 RE22}cores in 1–3 possess a ball-like structure with C3v symmetry, and can be viewed as consisting of an inner {RE22} core and an outer {Ni24} shell. From 1 and 2 to 3, due to the lanthanide contraction effect, the coordina -tion numbers for rare-earth metal centers in {RE22} are different, resulting in differ-ent number of SO42– and NO3– anions to support and stabilize the skeleton structures. Meanwhile, the magnetic properties of com-plexes 1–3 were also studied. The result revealed that complexes 1–3 show antiferromagnetic /ferrimagnetic interactions, and 3 ex-hibits magneto-caloric effect at ultralow temperatures with a maximum –ΔSm (magnetic entropy change) value of 33.03 J·kg−1 ·K−1 at 3.0 K and 7 T.

We detail the generation of a pulsed atomic oxygen (AO) broad beam with a high flux-density via collision-induced dissociation of O2 to support practical industrial exploitation of AOs, particularly for facilitating 2-dimenstional oxidation/etching at a fast rate of one-monolayer per second in an area ≥1000cm2. This innovation fuses the following interdisciplinary concepts: (a) a high density of O+ can be produced in an electron-cyclotron-resonance (ECR) O2 plasma; (b) O+ can be extracted and accelerated with an aperture-electrode in the plasma; (c) O+ with adequate kinetic energy can initiate a cascade of gas-phase collisions in the presence of O2; (d) collision-induced dissociation of O2 yields AOs with adequate kinetic energy which can cause additional collision-induced dissociation of O2. Computational simulations of such collisions, with both ab initio molecular dynamics and direct simulation Monte Carlo methods, are used to guide the experimental generation of the proposed AO-beam. We experimentally demonstrate the highest known AO mean flux-density of about 1.5×1016 atoms cm-2 s-1 in a broad-beam, and use it to oxidatively modify a self-assembled molecular layer of siloxane on a silicon wafer. In addition, we also demonstrate the growth of Al2O3 through an AO-assisted atomic layer deposition process at a room temperature.

Molecular ferroelastic with the natural features of mechanical flexibility and switchable spontaneous strain have attracted widespread attention in the scientific community due to their potential applications in tunable gratings, flexible memorizers, strain sensors, and intelligent actuators. However, most designs of molecular ferroelastics remain in the stage of blind exploration, posing a challenge to achieve a functional ferroelastic more effectively. Herein, we have successfully obtained a molecular ferroelastic, [Me2NH(CH2)2NH3](ReO4)2 (Me2NH(CH2)2NH3 = N,N-dimethylethylenediammonium), under the guidance of the mono-/double-protonating strategy. The double-protonated [Me2NH(CH2)2NH3](ReO4)2 undergoes a paraelastic-ferroelastic phase transition with the Aizu notation of 2/mF-1 at 322 K. Meanwhile, the theoretical calculation and experimental measurement simultaneously show that [Me2NH(CH2)2NH3](ReO4)2 possesses good mechanical flexibility, because its elastic modulus (E) of 8.26 GPa and hardness (H) of 0.45 GPa is smaller than the average value of organic crystals (E of 12.05 GPa and H of 0.5 GPa), which makes it promising to apply in wearable pressure sensors, implantable medical sensors, high-precision tuners, etc. This work further enriches the molecular ferroelastic family and demonstrates that mono-/double-protonation is one of the effective molecular modification strategies for designing ferroelastics.

Although, great achievements have been made in the synthesis of heterocycles using radical addition/cyclization strategy, developing versatile alkyl radical precursors, especially the non-stabilized ones for this method still remains a huge challenge. Herein, we report an efficient annulation cascade reaction between cyclosulfonium salts and alkenes for the synthesis of sulfur-containing N-heterocycles by visible light/copper catalysis under mild conditions. The C−S bond cleavage/radical cascade reaction delivers a variety of corresponding N-heterocycles containing aryl alkyl thioether motifs with good functional group tolerance. Significantly, the current system could be used for the late-stage functionalization of complex bioactive molecules.

The development of efficient and sustainable methods to obtain spirocyclic compounds is of significance as these structures are widely found in pharmaceuticals and agrochemicals. Herein, we disclose an electrochemical dearomative spirocyclization of N-acyl sulfonamides in a continuous-flow cell. The reaction is simple and efficient without external catalysts or supporting electrolytes, in-cluding a decagram-scale synthesis.

Polymer mechanochemistry on reactive species has attracted more and more attentions over the past 20 years, as the mechanochemical generation of reactive species has a great potential in developing different polymeric materials for various proposes, such as stress detection, self-healing, self-strengthening, controllable degradation and release of small molecules. In this review, we first discuss the recent progress on polymer mechanochemistry of the reactive species that are generated from the mechanochemical reactions of mechanophores. Five types of reactive species, including radical, zwitterion, ionic, carbene and neutral intermediates, and their applications were reviewed in detail. Since mechanochemical reactions are sensitive to the mechanophore structure and polymer framework, we then discuss how mechanophore isomerism, polymer structure, polymer attachment point, and polymer architecture influence the mechanophore activation. At last, we provide our perspectives on the polymer mechanochemistry of reactive species.

A disposable monolithic column mass spectrometry kit was developed based on monolithic column for microsampling, purification, storage, transportation and direct MS analysis of whole blood. The kit mainly consists of a capillary for quantitative microsampling of very small amount of blood (2 μL), a cation exchange monolithic column for purification and storage, and a syringe for loading sample. The cost of the kit is estimated to only one dollar. This MS kit is very friendly to various users that one can easily siphon small amount blood in the kit followed by rapid sample clean-up in 30s. We established a rapid quantitative method using the kit with a limit detection as low as 0.33 nM, achieved more than five orders of magnitude enhancement in MS analysis sensitivity compared to nanoelectrospray ionization MS analysis. The kit can avoid analyte exposure to oxygen, moisture and sunlight, which helps the storage of the sample. The relative standard deviation within 10 days were less than 10%. This method has been successfully applied to the quantitative analysis of procainamide hydrochloride in 2 μL rat blood. These results indicate that this kit does have the potential to achieve low-cost, highly sensitive quantitative MS analysis of biological sample.

Stability against oxygen is an important factor affecting the performance of organic semiconductor devices. Improving photooxidation stability can prolong the service life of the device and maintain the mechanical and photoelectric properties of the device. Generally, various encapsulation methods from molecular structure to macroscopic device level are used to improve photooxidation stability. Here, we adopted a crystallization strategy to allow 14H-spiro[dibenzo[c,h]a-cridine-7,9′-uorene] (SFDBA) to pack tightly to resist fluo-rescence decay caused by oxidation. In this case, the inert group of SFDBA acts as a “steric armor”, protecting the photosensitive group from being attacked by oxygen. Therefore, compared with the fluorescence quenching of SFDBA powder under two hours of sunlight, SFDBA crystal can maintain its fluorescence emission for more than eight hours under the same conditions. Furthermore, the photolu-minescence quantum yields (PLQYs) of the crystalline film is 327.37 % higher than that of the amorphous film. It shows that the crystal-lization strategy is an effective method to resist oxidation.

The Pd-catalyzed dipolar cycloaddition represents a significant synthetic strategy for the construction of useful heterocyclic com-pounds. This study developed the dipolar [4+2] and [6+2] cycloaddition reactions of benzo[d]isothiazole 1,1-dioxides (BDs) leading to the synthesis of BD-fused 1,3-oxazinane and 1,3-oxazocane derivatives, respectively. In particular, the synthesis of BD-fused 1,3-oxazinanes demonstrated regio- and enantioselective characteristics, resulting in products with good yields, enantioselectivity and regioselectivity (if applicable). Furthermore, the [6+2] cycloaddition reaction developed in this work represented the first strat-egy for the synthesis of medium-sized ring compounds based on BDs.