Chinese Journal of Chemistry最新文献

The development of solid-state protonic electrolyte is essential for safe and durable energy storage, yet their practical application remains limited by insufficient proton conductivity and narrow electrochemical stability windows. Although covalent organic frameworks (COFs) have emerged as promising platform for proton conduction owing to their ordered porous channels and tunable functionalities, conventional solvothermal synthesis generally requires harsh conditions, long reaction times, and large amounts of organic solvents. Herein, we report a simple and efficient mechanochemical ball-milling strategy for facile synthesis of a phosphoric acid-loaded COF protonic electrolyte (PA@TP-COF). Benefiting from the ordered nanochannels of TP-COF and the strong acid-base interactions between the framework and H₃PO₄, continuous hydrogen-bonding networks are constructed to facilitate efficient proton transport. Consequently, the PA@TP-COF electrolyte exhibits a high proton conductivity of 6.24 × 10⁻² S·cm⁻¹ with a low activation energy of 0.14 eV. Moreover, the electrolyte delivers a wide electrochemical stability window of 5.6 V. Solid-state proton batteries assembled with PA@TP-COF electrolyte achieve remarkable cycling durability with 72.2% capacity retention after 1500 cycles at 1.0 A·g⁻¹, together with excellent rate capability.

Efficient interfacial charge transport is essential for achieving high-performance organic solar cells (OSCs), while conventional cathode interlayers (CILs) often suffer from limited thickness tolerance due to insufficient vertical electron transport. Herein, we develop two hyperbranched CIL molecules, TPA-PDINNBr and BTT-PDINNBr, by integrating quaternized perylene diimide (PDI) units with three-dimensional triphenylamine (TPA) or benzo[1,2-b:3,4-b′:5,6-b″]trithiophene (BTT) cores. The three-dimensional molecular architectures preserve the intrinsic electron-transporting capability of PDI while constructing multidirectional charge-transport pathways and regulating molecular packing. Among them, BTT-PDINNBr exhibits enhanced conductivity (2.03 × 10^–4 S·cm^–1) and electron mobility (3.36 × 10^–3 cm²·V^–1·s^–1), resulting from the optimized balance between molecular ordering and three-dimensional transport. Incorporation of BTT-PDINNBr into PM6:D18:L8-BO OSCs delivers a high power conversion efficiency of 19.68% and maintains ~87% of the optimal efficiency with interlayer thicknesses exceeding 50 nm. This work provides a molecular design strategy for robust CILs by highlighting the importance of three-dimensional conductive networks and controlled solid-state packing for scalable and efficient OSCs.

Sulfonyl groups represent one of the most encountered structural motifs in medicinal chemistry. They serve as stable linkers that connect pharmacophoric elements within a molecule and as modulators of physicochemical properties, including lipophilicity, conformational flexibility, and metabolic susceptibility. This versatility makes sulfonyl-containing compounds highly attractive in drug discovery campaigns, particularly for protease inhibitors, kinase modulators, and covalent inhibitors. Among the various sulfonyl derivatives, sulfonyl fluorides have garnered interest due to their stability under ambient conditions and their ability to participate in sulfur(VI) fluoride exchange (SuFEx) reactions. Despite these advantages, the practical synthesis of sulfonyl fluorides remains a significant bottleneck. Conventional methodologies, such as oxidation of thiols or fluorination of sulfonyl chlorides, often suffer from narrow substrate scopes, incompatibility with sensitive functional groups, harsh reaction conditions and unsatisfactory regioselectivity when applied to polyfunctionalized molecules. These limitations severely impede the rapid assembly of sulfonyl fluoride libraries for biological screening and late-stage functionalization of complex drug candidates. To address this unmet need, we have developed a nickel-catalyzed Negishi cross-coupling protocol that utilizes bromomethyl sulfonyl fluoride (BMSF) as a readily available radical precursor. This approach enables the efficient construction of phenylmethylsulfonyl fluorides. The reaction proceeds under remarkably mild conditions, operates with high catalytic efficiency, tolerates a broad array of functional groups and exhibits excellent site selectivity even in the presence of multiple reactive sites. The synthetic utility of this method is further demonstrated by the facile conversion of the obtained products into a diverse range of sulfonamide derivatives through simple nucleophilic substitution reactions. This modular transformation provides a straightforward and scalable route to sulfonyl-linked molecular architectures, thus offering a versatile platform for medicinal chemistry efforts.

gem-Bis(silanes) have attracted significant attention due to their unique reactivity and functionality. Herein, we report a highly efficient Co/Ni-catalyzed dehydrogenative silylation/hydrosilylation reaction of alkenes for the construction of gem-bis(silanes). The unanticipated nickel impurities efficiently drive the key hydrosilylation step, enabling a high turnover number (TON) of up to 24,000. This reactivity represents the highest TON achieved for nickel-catalyzed hydrosilylation of alkenes. Mechanistic studies have revealed that the silicon-based directing effect plays a crucial role in governing both the reactivity and selectivity of this process. Furthermore, by controlling the nature of the nickel–hydride species, the key hydrosilylation step can be switched between geminal and vicinal pathways.

Given the well-established pharmacological significance of both imidazolidine derivatives and benzosultam analogues, the imidazolidine-fused benzosultam scaffold, which is accessible through molecular hybridization, represents an architecturally novel N-heterocyclic framework with substantial potential for medicinal chemistry research. Herein, we report an efficient protocol for the synthesis of highly substituted imidazolidine-fused benzosultams via a mild, catalyst-free [3+2] cycloaddition between readily available para-quinamines and cyclic N-sulfonyl ketimines. This transformation enables the convergent assembly of two privileged pharmacophoric motifs into a single polycyclic scaffold, and is characterized by high yields (up to 99%), remarkably broad substrate scope, excellent functional group tolerance, exceptionally fast reaction rates (complete within 5 min), and high diastereoselectivity. Notably, the purification can be accomplished simply by trituration, which significantly enhances both operational simplicity and environmental sustainability. Furthermore, for the first time, a bifunctional amine-thiourea catalyst has been successfully applied to the cycloaddition of para-quinamines, enabling a catalytic asymmetric variant that delivers structurally unprecedented enantioenriched 6/5/6/6-fused benzosultams in up to 90% yields with excellent diastereo- and enantiocontrol (up to 97.5 : 2.5 er). The practical utility of this methodology is demonstrated through scale-up synthesis and late-stage modification. Mechanistic investigations suggest the involvement of a single amine-thiourea catalyst in the enantiodetermining transition state, and two plausible mechanisms, along with their corresponding asymmetric induction models, are proposed. Collectively, this methodology provides a versatile platform for the rapid construction of imidazolidine and benzosultam bioisosteres, and holds great promise for applications in medicinal chemistry.

Structural design plays a pivotal role in the development of borate optical materials. In this work, fluorine acts as a "chemical scissor" to drive the continuous evolution of Sc-centered coordination polyhedra, and under this scissor's precise steering, three novel rare-earth scandium borate (fluoride) crystals, RbBaSc(BO₃)₂, RbBaSc(B₂O₅)F₂ and Ba₃Sc₂(BO₃)₂(B₂O₅)F₂, were rationally designed and synthesized via high-temperature solid-phase synthesis. Structural analysis reveals a two-step structural iteration process of the Sc-centered polyhedra from [ScO₆] to [ScO₄F₂] and finally to [ScO₅F], while the favorable alignment of birefringence-active B–O motifs is retained in the final ordered phase. Notably, Ba₃Sc₂(BO₃)₂(B₂O₅)F₂ exhibits a UV cutoff edge below 200 nm and a calculated birefringence of 0.078 at 546 nm, demonstrating how the fluorine-driven evolution of Sc-centered polyhedra effectively enhances optical anisotropy while preserving deep-UV transparency. This work provides strong structural evidence for understanding fluorination-driven coordination reconstruction and framework evolution in borate optical materials.

Biological ion channels regulate ion flux through gating and blockade, yet translating such precise kinetic control into discrete synthetic containers remains a fundamental challenge in supramolecular chemistry. Here we report a bioinspired calix[4]trap ion container engineered with a crown ether binding site at its aperture to implement ion controlled gating. Specifically, K⁺ and NH₄⁺ occupy a deeply buried pocket, whereas Cs⁺ preferentially and exclusively binds at the entrance, acting as a removable gatekeeping ion that restricts access to the cavity. Consequently, Cs⁺ bound at the entrance hinders both ion encapsulation and release, enabling direct observation of otherwise rapid uptake processes and providing a quantitative handle to decelerate release. Importantly, the release kinetics are strictly decoupled from the thermodynamic driving force. The release rate is governed by the concentration of the gatekeeping Cs⁺ rather than the stoichiometric amount of the chemical trigger (DBU). This allows for sustained and programmable ion release over hours through a simple stoichiometric input. This minimal noncovalent gatekeeping strategy offers a general blueprint for designing tunable ion carrier containers and programmable biomimetic transport systems.