The application of two-dimensional (2D) MXenes for interface modification has been demonstrated as an effective strategy to improve the performance of perovskite solar cells (PSCs). However, the strong van der Waals interactions among MXene nanosheets lead to aggregation and poor film uniformity during spin-coating. To address this, we blend Ti₃C₂T_x MXene with polyethylene glycol (PEG) as a dispersant and film-forming agent, enabling uniform and continuous film coverage. The resulting PEG-MXene composite forms a uniform buried interlayer between the SnO₂ ETL and the perovskite absorber, which effectively passivates interfacial defects, optimizes energy level alignment, and guides perovskite crystallization. Benefiting from this synergistic modification, the corresponding devices achieve a champion power conversion efficiency (PCE) of 24.76% along with enhanced operational stability under continuous illumination and thermal stress at 70 °C. Notably, the incorporation of PEG significantly improves the reproducibility of device fabrication, enabling a PCE of 20.06% in large-area devices (1.0 cm²), thereby affirming its potential for scalable manufacturing of PSCs.

Planar–chiral compounds have garnered significant interest due to their unique stereochemical features and promising applications in asymmetric catalysis, materials science, and molecular recognition. To date, only a few representative classes have been discovered and synthesized, including planar-chiral cyclophanes, ferrocenes, and macrocyclic hosts such as pillararenes and calixarenes. The construction of novel planar-chiral architectures therefore continues to pose a formidable challenge. Herein, we present a simple but highly effective approach for constructing a new form of planar chirality through the formation of three-dimensional double-layered cyclic molecular architectures. Photocycloaddition of C=C double bonds embedded within benzo[b]thiophene 1,1-dioxide affords trans Z-type (Trans-1) and cis-∏-type (Cis-Rac-1) dimers. While Trans-1 is achiral owing to its central symmetry, Cis-Rac-1 adopts a distinctive bisplanar geometry that gives rise to an unprecedented type of planar chirality. The enantiomers of Cis-Rac-1 are successfully resolved via chiral high-performance liquid chromatography. Circular dichroism spectroscopy and single-crystal X-ray diffraction unequivocally confirm the planar–chiral nature of these enantiomers. Moreover, both experimental and computational results show that the planar chirality is highly stable, with a racemization barrier exceeding 35 kcal/mol. These findings establish a general and straightforward strategy for construction of planar chirality, opening new avenues for the design of planar–chiral functional materials.

The integration of protection chemistry with desymmetrization or kinetic resolution has emerged as a powerful tool for the construction of optically active compounds. Over the past two decades, a variety of enantioselective silyl protection methodologies have been established through transition-metal catalysis, organocatalysis, and enzymatic catalysis. To further expand the scope of enantioselective protection strategies, our group recently proposed a Lewis base-catalyzed enantioselective Boc protection approach using readily available di-tert-butyl dicarbonate (Boc₂O). Based on this concept, we have developed isothiourea- and biscinchona alkaloid-catalyzed atroposelective O-Boc protection reactions for the synthesis of axially chiral compounds. Meanwhile, organosilicon compounds featuring a stereogenic silicon center have drawn considerable attention due to their promising applications as chiral reagents, pharmaceuticals, and functional materials. However, in the field of enantioselective protection chemistry, only a few O-silyl protection strategies have been reported to access silicon-stereogenic silanols. Herein, as a continuation of our efforts to extend enantioselective Boc protection to other forms of chirality, we report a biscinchona alkaloid-catalyzed enantioselective O-Boc protection protocol for the preparation of silicon-stereogenic organosilanes. In the presence of a commercially available Lewis base catalyst, two identical phenolic groups tethered to a silicon center are effectively discriminated to react with Boc₂O, delivering enantioenriched organosilanes bearing a silicon stereocenter in good to excellent yields with high enantioselectivities. This desymmetrization process is readily scalable to gram quantities without significant loss of efficiency. Combined with the low cost and easy availability of the catalyst and reagent, this method offers a practical approach to silicon-stereogenic molecules. Furthermore, the resulting products can be conveniently transformed into silicon-stereogenic phosphines through downstream derivatizations, and preliminary studies indicate their potential application as chiral ligands in Pd-catalyzed asymmetric allylic alkylation of diethyl malonate.

Efficient Xe/Kr adsorption-based separation is highly desirable as an energy-saving alternative to cryogenic distillation for producing high-purity xenon. However, the similar physicochemical properties of xenon and krypton make selective separation challenging, requiring precise regulation of pore size and host-guest interactions. Herein, a series of alkoxy-functionalized three-dimensional covalent organic frameworks (COFs) with a 7-fold interpenetrated pts topology are designed and synthesized. By varying the alkoxy chain length, the sub-nanometer pore environment and xenon-binding sites are systematically tuned, leading to COFs with adjustable Xe/Kr separation performance. Gas adsorption results show an enhanced xenon affinity with increasing alkoxy chain length. Among them, 3D-TAPB-(OEt)₃-COF exhibits the highest Xe/Kr selectivity of 9.92 at 273 K and 1 bar, which is attributed to its optimized micropore size and abundant alkoxy groups. Theoretical calculations suggest that multiple alkoxy groups and extended alkyl chains strengthen xenon adsorption through enhanced van der Waals interactions. Dynamic breakthrough experiments further confirm the effective separation of Xe/Kr mixtures. This study highlights alkoxylation-based functional group regulation as an effective strategy for tailoring sub-nanometer pore environments in COFs toward noble gas separation.

Conjugated polymers are promising platforms for integrated optoelectronics, yet in most reported high mobility diketopyrrolopyrrole (DPP)-based semiconductors, strong intermolecular aggregation and narrow bandgaps suppress luminescence, limiting their applicability in multifunctional devices. The concurrent realization of efficient charge transport and strong thin film emission therefore remains a fundamental challenge. Here, we report two novel DPP-derived polymers, PTFBVDPP-V and PTFBVDPP-TVT, synthesized via Stille coupling through precise donor-acceptor (D-A) engineering. Both polymers possess highly coplanar backbones, forming continuous fiber networks and ordered crystalline films with close intermolecular π-π stacking. Polymer PTFBVDPP-V functions as a unipolar n-type semiconductor with an electron mobility (μ_e) of 2.61 cm²·V⁻¹·s⁻¹ but negligible emission. In contrast, precise D–A modulation in PTFBVDPP-TVT enables balanced ambipolar transport with a hole mobility of 1.52 cm²·V⁻¹·s⁻¹ and an electron mobility of 1.15 cm²·V⁻¹·s⁻¹, while retaining a thin-film photoluminescence quantum yield (Φ) of 6.5%. This combination delivers a maximum Φ·μ_e exceeding 10⁻² cm²·V⁻¹·s⁻¹, establishing a record performance among high-mobility ambipolar emissive polymer semiconductors and breaking the long-standing trade-off between charge transport and luminescence in conventional high-mobility DPP-based systems.

The alkene hydroarylation reaction is among the most powerful and atom-economical methodologies in modern organic chemistry to straightforwardly construct the C(sp²)−C(sp³) bonds and the C(sp³)−H bonds for the selective incorporation of aryl groups into the two olefinic carbon sites leading to valuable complex aryl-based alkane molecules, which have been proven to be instrumental in the synthesis of many natural products, pharmaceuticals and organic functional materials. Herein, we describe a synergetic photoredox and CO₂^•− catalysis for a regioselective hydroarylation of 1-alkenyl carbonyls with cyano(hetero)aromatics via radical anion sorting. Using the carbon dioxide radical anion (CO₂^•−) as a powerful single electron reductant in cooperation 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.

Substituted pyrans are prevalent structural motifs in natural products and bioactive molecules, and their enantioselective synthesis remains an important objective in organic chemistry. Herein, we report a rhodium(I)-catalyzed enantioselective intramolecular [2+2+2] cyclization of yne-enones for the efficient construction of chiral substituted pyrans. Using a commercially available SDP ligand, this transformation proceeds under mild conditions and exhibits good substrate scope, delivering bicyclic pyran derivatives in moderate to good yields with excellent enantioselectivities (up to 98% ee). The transformation proceeds via Rh(I)-mediated oxidative cyclization to form a chiral rhodacycle, followed by carbonyl insertion and reductive elimination to deliver the pyran scaffold. The synthetic utility of this methodology is further demonstrated by a one-pot cyclization/hydrolysis sequence. Treatment of the in situ generated pyran intermediates with Sc(OTf)₃ enables efficient conversion to optically enriched 1,5-diketones bearing two contiguous stereocenters, with high enantioselectivity and moderate diastereoselectivity. Control experiments support a stepwise process involving pyran formation followed by Lewis acid-promoted ring opening. Overall, this work provides an efficient and versatile strategy for the asymmetric synthesis of substituted pyrans and related chiral 1,5-dicarbonyl compounds. The combination of high enantioselectivity, operational simplicity, and broad applicability highlights the potential of this methodology for applications in complex molecule synthesis and asymmetric catalysis.

Transition-metal-catalyzed reductive coupling of unactivated alkenyl carbamates remains challenging due to the high bond dissociation energy of the C(sp²)–O bond. By designing a remote directing strategy based on noncovalent interactions involving aromatic π-system, we herein report an iron-catalyzed reductive cross-coupling reaction that enables the efficient coupling of alkenyl carbamates derived from cyclohexene frameworks with alkyl bromides within an iron/diboron catalytic system. Mechanistic studies suggest that this transformation is facilitated by a C–H–π interaction between the pendant aryl moiety on the cyclohexene substrate and a C–H bond on the ligand, while an iron(I) species likely serving as the catalytically active intermediate. These findings provide insights into iron-catalyzed activation of unactivated C(sp²)–O bonds and may open avenues for the development of transformations of other chemical bonds via remote directing strategies enabled by noncovalent interactions.

Excessive intermolecular aggregation and crystallinity mismatch between donor and acceptor materials in binary blend system give rise to incompatible crystallization kinetics and insufficiently interconnected domains, which impede charge transport and limit the improvement of power conversion efficiency (PCE). Herein, a novel multi-arm polymer was developed based on BDT and BDD units. Characterized by a large conjugated plane and a three-dimensional molecular conformation, H21 not only complements the energy levels and absorption profile of the host system but also enhances charge generation and transport. More importantly, H21 can function as an effective seeding agent, regulating crystallization processes, suppressing over-aggregation, and strengthening donor-acceptor interactions within the active layer. As a result, the optimized ternary blend containing 10 wt% H21 demonstrates refined nanoscale phase separation and improved molecular ordering, leading to an excellent PCE of 19.70% in the D18:H21(10%):L8-BO-based ternary device. This work demonstrates that judiciously introducing multi-arm molecular seeding agents represents a promising strategy for modulating morphology and intermolecular interactions toward high-performance PSCs.

Nanostructured island-confined metal catalysts offer remarkable stability; however, it is challenge to balance the activity and selectivity in multi-step reactions owing to the limited electronic modifications for individual metal systems. Here, we develop a strategy by integrating “nano-island confinement” with “dilute alloying”, in which ~0.7 nm Pt₉₅Cu₅ dilute alloy clusters are confined onto CeO_x nano-islands. As expected, this confinement not only suppresses metal migration and leaching, but also tailors the surface electronic structure via strong Pt-Cu coupling to regulate substrate adsorption and activation. Various characterizations reveal that the as-designed catalytic system maintains abundant active sites because of the nearly full exposure of Pt, and more importantly, downshifts the Pt d-band center through d-d hybridization within Pt-Cu dilute alloy. As a result, this configuration optimizes furfural adsorption behavior, and favors its planar adsorption instead of vertical one. DFT calculation further shows that planar-adsorption-driven hydrogenation remarkably enhances the reaction kinetics by reducing the barrier for FurCH₂O formation and accelerating proton-coupled electron transfer step. Compared with nano-island confined Pt catalyst, the confined Pt-Cu dilute alloy increases the TOF for furfural conversion from 849.3 to 1008.7 h^–1 and for furfuryl alcohol from 383.9 to 657.7 h^–1, and demonstrates remarkable stability under demanding conditions (150 °C, 3 MPa H₂). These results demonstrate that the nano-islands confined dilute alloy strategy is promising for effectively maintaining metal stability and adjusting activity-selectivity balance.

Supramolecular macrocycles, despite their ubiquity in molecular recognition, have remained largely unexplored in photocatalysis due to their intrinsic lack of continuous π-conjugation and inefficient charge-carrier separation. Here, we report a conformational engineering strategy to integrate dynamic B←N dative bonds into highly active photocatalytic macrocyclic architectures. By simply switching the boronate linker from meta to para geometry, we control the rotational freedom of B←N bonds to yield two isomeric frameworks-twisted BNF-80 and planar BNF-81-with well-defined supramolecular macrocyclic building units, as unequivocally confirmed by single-crystal X-ray diffraction. The planarized conformation of BNF-81 enforces extended π-conjugation and continuous π-π stacking, leading to markedly enhanced charge separation efficiency and charge transfer. As a result, BNF-81 achieves an outstanding photocatalytic H₂O₂ production rate of 4275 μmol·g^–1·h^–1 under visible light in pure water without any sacrificial agent, outperforming previously reported B←N-based photocatalysts. This work establishes linker conformation driven control as a powerful design principle, unlocking the latent photocatalytic potential of supramolecular macrocycles and opening a new avenue for developing efficient metal-free photocatalysts.

Efficient separation of C₂H₆ and C₃H₈ from CH₄ remains a significant challenge due to their similar molecular dimensions and nonpolar nature. This study resolves this bottleneck by realizing π-electron modulation of aromatic pore surfaces via strategic ligand functionalization. Three isostructural metal-organic frameworks with dia topology, namely Ni(3-fpba)₂, Ni(3-mpba)₂, and Ni(3-npba)₂, were synthesized with substituents of varying electronic characters. The progressive enhancement of electron-donating ability systematically enriches the π-electron density, which strengthens C–H···π interactions with alkane molecules in a size-discriminative manner. Notably, the amino-functionalized Ni(3-npba)₂ exhibits a C₂H₆ uptake of 80.5 cm³·g^–1 at 273 K and 10 kPa, representing a 96% enhancement over its fluorinated counterpart while maintaining negligible CH₄ adsorption. This performance leads to IAST selectivities of 30.4 for C₂H₆/CH₄ and 398 for C₃H₈/CH₄, surpassing most benchmark materials. Dynamic breakthrough experiments and GCMC simulations collectively reveal that enhanced π-electron density intensifies host-guest charge redistribution. These findings establish aromatic π-electron density as a tunable descriptor for the rational design of natural gas purification materials.

Sulfoxides are structural motifs widely found in natural products and bioactive molecules, while also serving as linchpins for organosulfur compound preparation and as ligands or directing groups for transition-metal-catalyzed transformations. This makes their synthesis a long-standing focus of research. Over the past five years, sulfinylation using readily available sulfinates has proven to be a promising strategy for introducing sulfinyl groups into molecules. In this context, alkyl alcohols have been commonly employed as nucleophiles to react with sulfinates and acylating reagents, enabling the synthesis of sulfinate esters and their chiral variants. However, the potential of alkyl alcohols to act directly as radical precursors in sulfinylation remains unexplored. Herein, we report the first photocatalytic ring-opening sulfinylation of strained cycloalkanols, offering a direct route to sulfoxides with a remote carbonyl group that were traditionally accessed via sequential thioether synthesis and mono-oxidation. In this protocol, with an appropriate acylating reagent, both aryl and alkyl sulfinates are competent substrates. Mechanistically, organic photocatalysis promotes the generation of alkoxy radicals from cyclopropanols and cyclobutanols. The high ring strain of these alkoxy radicals drives a fast β-scission process, furnishing transient alkyl radicals. Subsequent radical substitution with in situ generated sulfinyl sulfones (from sulfinates and acylating reagent) delivers γ- and δ-keto sulfoxides. This one-pot method is characterized by mild reaction conditions, readily available sulfinyl sources and good chemoselectivity. The carbonyl and sulfinyl moieties in the products proved amenable to further derivatization, as shown by a series of well-established transformations.

Asymmetric B–H bond insertion reactions of carbenes represent the most straightforward route to access organoboron compounds. We herein present a chiral dirhodium-catalyzed B−H bond insertion reaction of vinylcarbenes that enables direct access to enantioenriched α-trifluoromethyl allylboranes from readily accessible amine-borane adducts and triftosylhydrazones. This operationally simple protocol exhibits broad substrate scope and functional group tolerance, delivering optically active α-trifluoromethyl allylboranes with good to high yields and enantioselectivities. Additionally, we showcase the utility of this method through two functional group transformations. Combined experimental and computational studies provide insights into the origin of enantioselectivity in the B–H bond insertion process.

A highly diastereoselective copper-catalyzed defluorosilylation of pentafluoroethyl alkenes is described. In the presence of CuCN/PCy₃ catalyst, polyfluorinated allylsilanes containing an sp²-carbon connected to F and CF₃ can be synthesized with E-alkene geometry. Without the ligand, the Z-alkenes are obtained as major products. Moreover, a one-pot defluorosilylation/protodesilylation sequence affords the hydrodefluorination product, which can undergo another round of defluorosilylation to generate trifluoromethylated allylsilanes as Z-alkenes.

Halogenation plays a crucial role in organic synthesis. Over the past century, numerous reaction systems have been developed for the synthesis of halogen-containing molecules. However, traditional halogenation reactions rely on highly reactive halogenating reagents, suffer from poor regioselectivity and limited functional group tolerance. In 2015, Jiao et al. from Peking University achieved the efficient oxidative bromination of (hetero)arenes and alkenes using a mild reaction system consisting of stoichiometric amounts of dimethyl sulfoxide (DMSO) and aqueous hydrobromic acid (Jiao Bromination). Following in-depth research on Lewis base activation systems, Jiao and coworkers further developed a DMSO-catalyzed chlorination of (hetero)arenes using N-chlorosuccinimide (NCS), which enables the late-stage modification of complex molecules (Jiao Chlorination). Their works clarify that DMSO plays distinct roles at different loadings: stoichiometric DMSO acts as a mild oxidant to drive oxidative bromination with hydrobromic acid, catalytic DMSO serves as a Lewis base catalyst to activate NCS for selective chlorination, and excess DMSO forms an inert (DMSO)_n•X⁺ adduct to inhibit reaction activity. The theoretical framework promotes the innovation of halogenation strategies. Jiao halogenation has been widely applied to various fields of organic synthesis, including late-stage modification of bioactive compounds, total synthesis of natural products, and preparation of material molecules.

Theranostics combines diagnostic and therapeutic functions to enable personalized treatment strategies in precision medicine. Metal-organic frameworks (MOFs) have emerged as promising platforms for such applications due to their tunable porosity and multifunctionality. Noncovalent interactions, including hydrogen bonding, π–π stacking, electrostatic forces, and hydrophobic effects, play crucial roles in governing drug loading, stimuli-responsive release, and structural stability of these systems. This review examines the mechanistic contributions of noncovalent interactions in MOF-based theranostics and explores how machine learning approaches can facilitate rational design through systematic analysis of interaction patterns. We survey recent applications in treating cancer, infectious diseases, cardiovascular disorders, and metabolic conditions. Current challenges and future opportunities are discussed, including artificial intelligence (AI)-assisted design strategies, integration of multimodal theranostic functions, and pathways toward clinical implementation.

Metal–organic frameworks (MOFs) have shown great potential as highly ordered porous materials in biomedical applications. However, the perfect crystalline structure of conventional MOFs often leads to limitations such as rigid active sites, restricted mass transport, and insufficient loading capacity. Defect engineering, through the intentional introduction of structural defects (such as missing-linker and missing-cluster), has emerged as an important strategy to overcome these constraints. It can significantly expand pore volumes, enhance surface accessibility, and endow the materials with enzyme-mimicking activities. Despite the rapid development of Defect-Engineered MOFs, a systematic summary of the defect formation mechanisms, synthetic strategies, and roles in biomedical applications is still lacking. This review systematically outlines the synthetic strategies for Defect-Engineered MOFs, discusses the relationships between the structure and performance, and highlights representative advances in drug delivery and all-in-one tumor therapeutic. Finally, we discuss the challenges regarding reproducibility and biocompatibility in the field, and propose future directions for promoting the clinical application of Defect-Engineered MOFs.

In 1989, Robson developed the first MOFs by varying the building blocks, specific substances can be captured and stored inside the cavities. Following pioneering work by Robson, around the turn of the 2000s, Kitagawa and Yaghi developed more flexible and stable MOFs, whose highly tunable and coordinatively flexible structure rapidly sparked widespread interest and laid the foundation for this rapidly expanding field of porous materials. In 1997, Lin and his coworkers researched coordination polymers. In 1998, they first reported a neutral three-dimensional iron coordination polymer. Since around 2004, the group has focused on biomedical applications of nanoscale MOFs. In 2006, Chen pioneered and validated the ligand-directed strategy, laying the foundation for the precise design of subsequent MOFs. In 2007, Bu reported a PCU-type MOF, achieving porosity and defect regulation. By 2008, Attfield used atomic force microscopy to reveal surface growth defects in HKUST-1, providing early insights into MOF crystallography defects, while Lillerud introduced the exceptionally stable UiO-66, a zirconium-based framework that later became a cornerstone material in both engineering and biomedical research. In the same year, Wang pioneered the design and regulation of colossal cages in ZIFs for gas storage. In 2009, Serre pioneered the flexible MIL series and systematically explored framework dynamics (breathing behavior), paving the way for applications in controlled drug delivery and other biomedical fields. A paradigm shift occurred in 2013 when Zhou directly demonstrated and quantified abundant missing-linker defects in UiO-66, establishing defects as a viable and powerful means of property modulation. In 2015, Fischer formally defined Defect Engineering as a core strategy for precisely tailoring MOF properties. Around 2016, Morris and coworkers developed effective top-down methods to controllably introduce and manipulate defects, strongly promoting defect-engineered MOFs in drug delivery research. In 2017, Forgan reported pioneering studies on MOF-based drug loading and controlled release; by 2020 his team achieved a major advance with defect-engineered systems enabling controlled co-delivery of multiple therapeutic agents. In 2019, Jiang used defect engineering to improve the catalytic performance of MOFs. In the same year, Zhao and collaborators introduced defect-engineered MOF nanozymes, significantly expanding MOF applications in catalytic nanomedicine, and later innovated asymmetric single-atom catalysis within defect-MOFs for synergistic tumor treatment. In 2020, Pang reported the introduction of quasi defects, to further enhance the enrichment and catalytic performance of MOFs. In the same year, Shi et al., reported MOF nanozymes for synergistic therapy. In 2021, Liu's team developed multifunctional theranostic platforms based on Defect-MOFs that seamlessly integrate imaging and therapy. In 2024, Ouyang pioneered the development of Defect-MOFs as nucleic acid hydrolase nanozymes. Most recently, in 2025, Leticia Hosta-Rigau and colleagues demonstrated defect-engineered MOFs for hemoglobin-based oxygen delivery, offering promising new approaches to relieve tumor hypoxia and reprogram the tumor microenvironment. Importantly, Zhao and Li et al. reported the design of MOF-based materials with multiple morphologies, providing a new approach for the design and application of novel Defect-MOFs.