ABSTRACT Covalent organic frameworks, with their tunable pore structures, chemical environments, and high stability, are promising candidates for next‐generation solid‐state battery separators. To uncover the fundamental Li + transport mechanisms and enable rational design, we performed high‐throughput molecular dynamics simulations and data‐driven screening on a library of 628 metallosalen‐based COFs across five representative lithium‐salt systems. Our results demonstrate that efficient Li + transport depends critically on matching the COF pore chemistry with anion characteristics: weakly coordinated BOB − anions favor lightweight, moderately confined pores, whereas flexible TFSI − anions perform better in large‐pore, open‐topology COFs. More importantly, our simulation data suggest a potential anion‐engaged cooperative transport mode. This mode is characterized by the formation of a dynamic coordination network when a significant proportion (> 50%) of anions exhibit spatially confined motion. These confined anions appear to repeatedly coordinate and release Li + ions, facilitating a relay‐style conduction along the pore channels. Simulation analyses indicate that this mode correlates with high Li + diffusion coefficients and uniform ionic flux. Based on these observations, we propose two material design guidelines: anion‐adaptive pore matching and confined‐anion dynamics regulation. This work offers a theoretical perspective and a computational screening strategy for the rational design of COF‐based solid electrolytes.
ABSTRACT Efficient photocatalytic H 2 O 2 production is a sustainable alternative to the anthraquinone process, yet designing photocatalysts with both high activity and selectivity is extremely challenging. Covalent organic frameworks (COFs) offer modular architectures and tunable electronic structures, but precise electronic modulation for maximizing H 2 O 2 photosynthesis is rarely attained. Here we report a series of naphthalimide‐based donor–acceptor COFs with systematically engineered cores. Among them, NDI–B–COF (benzene core) delivers an outstanding H 2 O 2 yield of 11,025 μmol g −1 h −1 (with sacrificial agent), far surpassing its nitrogen‐ and triazine‐core analogs. This performance stems from synergistic effects of an extended in‐plane conjugation and a reduced core polarity, which collectively enhance charge separation, directional carrier transport, and *OH intermediate formation, thereby lowering the barrier for two‐electron water oxidation. These findings establish a clear structure–property–activity correlation and offer a general strategy for developing highly efficient metal‐free photocatalysts.
ABSTRACT Achieving regioselective C–H functionalization is a particularly difficult issue in organic chemistry when these C–H bonds have similar reactivity. Although significant progress has been made in regioselective C–H functionalization at one specific site, the tunable version of such processes is rarely documented. Here we describe a tunable meta ‐ and para ‐selective C–H borylation of aryl and benzyl phosphonates, in which the regioselectivity can be switched by bifunctional ligands. A broad range of substrates are compatible and exhibit good to excellent regioselectivity under mild reaction conditions. Benzyl phosphonates can be conveniently transformed into styrene derivatives via Horner–Wadsworth–Emmons olefination. Gram‐scale preparation and derivatization of borylated products demonstrate the important application of our method in synthetic chemistry. The orthogonality of two functional Bpin and phosphorylmethyl groups provides ample opportunity for increasing the diversity of styrene derivatives with precise site‐control.
ABSTRACT Mechanical force redistributes reactivity through anisotropic, topology‐dependent load transmission. Predicting which covalent bond in a complex molecule ruptures first under tension remains a central problem in mechanochemistry, biomaterials and chemically recyclable polymers. Bond dissociation energy is an incomplete proxy because it describes zero‐force thermodynamic stability, whereas mechanochemical site selectivity is governed more directly by the peak force sustained along a prescribed loading path. Here we introduce covalent‐bond peak force network (CBPFNet), a graph‐attention model that predicts covalent‐bond peak force (CBPForce) from relaxed molecular structures through a virtual‐stretching workflow and avoids the hundreds of constrained geometry optimisations typically required for each candidate bond. In the CHON benchmark studied here, CBPFNet reproduces bond‐ranking trends from density functional theory (DFT) and can be used for bond‐level screening. Post hoc attribution analyses indicate that rupture selectivity depends on both bond identity and local stiffness contrast, with relatively rigid segments concentrating tensile stress on softer adjacent bonds. In oligopeptides, the model recovers the DFT weakest bond and highlights a serine‐containing motif as a possible topology‐dependent weak point under the same protocol. CBPFNet therefore extends screening beyond equilibrium bond stability toward bond‐resolved peak‐force ranking in sustainable polymer design and biomaterials.
Ambimodal transition states (TSs) lead to two or more products via post-transition state bifurcations (PTSB). Over the past decade, numerous examples of ambimodal cycloaddition reactions have been reported, and a number of these are involved in enzyme-catalyzed reactions in biosynthesis. This review covers enzymes known to catalyze [4 + 2]/[6 + 4] ambimodal cycloadditions, in which a single transition state leads to both [4 + 2] and [6 + 4] cycloaddition products. We also describe recent advances in computational methods for the study of bifurcations, and predictions of product ratios that are otherwise determined by calculating a large number of trajectories with quasi-classical molecular dynamics. These methods include entropy path sampling, and product distribution predictions with correlational methods.
Perovskite solar cells (PSCs) have emerged as transformative technology in the field of photovoltaics. Following their inception in year 2009, they have become within a decade the leading candidate for next-generation photovoltaics due to their exceptional efficiency, low-cost processing, and tunable optoelectronic properties. However, challenges surrounding long-term stability, lead toxicity, and industrial scalability remain major barriers to large-scale commercialization. This perspective explores the central role of materials innovation in overcoming these obstacles, focusing on advances in compositional engineering, molecular additives and passivation, interfacial chemistry, and 2D/quasi-2D perovskite systems. Particular attention is given to the evolution of charge transport architectures and the emerging commercial landscape. We also highlight the importance of shifting from performance-driven research to durability- and manufacturability-conscious strategies. The article concludes with recommendations for future directions in PSC development, including the need for standardized testing, predictive materials design, and environmentally responsible fabrication.
Biosynthesis, utilizing highly evolved enzymes, achieves exceptional efficiency and precise stereo-control under mild conditions. In contrast, chemical synthesis provides stability, flexibility, and broad applicability, enabling numerous transformations beyond natural metabolism. Although these two systems have complementary strengths and appear to operate under different synthetic philosophies, recent decades have revealed the exciting opportunities of integration strategy in molecular synthesis. Considering the fact that catalysis is the key of synthesis, this perspective highlights some representative examples in catalysis where chemistry and biology mutually inspire and extend one another. For chemical synthesis, biomimetic catalysis has evolved from coenzyme-inspired small-molecule systems to peptide frameworks and sophisticated metal complexes that replicate enzymatic logic, achieving efficiency and selectivity rivaling or surpassing natural enzymes. Conversely, chemical inspiration has reshaped biosynthesis through artificial metalloenzymes, enzyme repurposing, photoenzymatic catalysis, and dual chemo-biocatalysis, thereby greatly expanding enzymatic reactivity beyond nature's repertoire. Emerging technologies including de novo enzyme design, directed evolution, and gene editing are enabling the creation of new-to-nature functions. Despite significant progress, challenges remain in rational design, catalytic efficiency, system compatibility, and scalability. Yet the trajectory of this field points to a future where chemocatalysis and biocatalysis will no longer be dramatically distinct, rather, they will integrate into a compatible framework for sustainable molecular synthesis.
The development of stereospecific transformations of organoboron compounds has advanced rapidly over the past decade, driven by their exceptional configurational stability, tunable reactivity and broad functional group tolerance. Central to this progress is the use of ate complexes, generated by organolithium activation, which undergo highly enantiospecific reactions via either stereoretentive or stereoinvertive pathways. These strategies enable the efficient construction of new C–C, C–O, C–N, C–F, C–S and C–P bonds at stereogenic centres, often with complete preservation of enantiopurity. Reactivity can be further expanded through transmetalation to access more reactive organocopper and organozinc intermediates, unlocking transformations previously inaccessible to direct boronate chemistry. This review critically surveys recent advances in the stereospecific functionalisation of secondary, tertiary and polyboronic esters, emphasising applications in complex molecule synthesis and outlining key challenges ahead, including the stereocontrolled construction of quaternary centres, late-stage diversification and underexplored heteroatom couplings.
The activation and catalytic conversion of resource-abundant small molecules (e.g., H 2 O, N 2 , O 2 , CO 2 , and CH 4 ) hold transformative potential for synthesizing value-added chemicals and improving energy conversion/storage efficiency. However, these processes remain challenging owing to the high bond dissociation energy and low reaction selectivity of these molecules, making the development of advanced catalytic materials essential. In this perspective, we systematically review and summarize the small-molecule activation mechanisms on Mott–Schottky heterojunctions and intermetallic compounds, while discussing the critical role of small-molecule activation in energy storage applications. We also highlight the emerging impact of artificial intelligence in accelerating catalyst design and unraveling reaction mechanisms. Finally, we offer our perspectives on the key factors and future directions for advancing research in small-molecule activation.
Spin catalysis offers a new perspective for developing highly efficient catalytic reactions by leveraging electron angular momentum—another fundamental parameter controlling the chemical reaction. Electron spin plays a critical role in reactions including but not limited to electrochemistry, photochemistry, and organic synthesis. However, the correlation between spin state and reaction efficiency remains incompletely elucidated, which hinders the advancement in this field. The unique capabilities of single-molecule platforms enable real-time spin-state observation and precise manipulation, thus inspiring the exploration of their potential to advance spin catalysis. Accordingly, this perspective examines the prospects of single-molecule platforms in spin catalysis, with the goal of fostering interdisciplinary research to elucidate the mechanism of spin catalysis and develop novel synthesis methodologies based on precise control of spin states. We first discuss the influence of electron spin on spin-dependent reaction thermodynamics and kinetics, along with effective approaches to achieve spin manipulation. Building on this foundation, we summarize key challenges and opportunities in spin catalysis and evaluate the potential of single-molecule platforms for mechanistic studies and precision synthesis in spin catalysis, including efficient spin injection, precise spin-state detection, and coherent spin manipulation.
Advances in material science have intensified the focus on structure–activity relationships (SAR), with big data models facilitating more efficient SAR analysis. Skeletal editing enables precise atomic-level modification of structural cores, facilitating the direct construction of complex molecules. However, editing simple isoquinolines into more complex π-extended phenanthridines via a one-pot process remains unexplored. These π-extended phenanthridines are significant in material science and medicinal chemistry due to their unique structural characteristics and photophysical properties. Herein, we report the first skeletal editing methodology for rapidly transforming readily available isoquinolines into (dihydrodibenzo[ c , i ]phenanthridin-6-yl)diphenylphosphine oxides (DHBPPO) derivatives. These DHBPPO derivatives exhibit tunable emission, aggregation-induced emission (AIE) properties, organelle-targeted specificity, and significant anti-tumor activity in vitro. Our findings provide a promising platform for SAR studies and the development of new luminescent functional materials.
The development of chiral heterogeneous catalysts that combine high activity, stability, and stereoselectivity remains a central challenge in asymmetric catalysis. Traditional strategies that immobilize chiral molecular catalysts on amorphous supports typically suffer from non-uniform active site distribution, poorly defined local environments, and catalyst leaching, which collectively compromise stereocontrol and long-term stability. Crystallizing chiral molecular catalysts within metal–organic frameworks (MOFs) offers a transformative solution. The inherent crystallinity of MOFs ensures deterministic positioning and uniform distribution of catalytic sites, effectively propagating chirality throughout the framework. Site isolation stabilizes active species and prevents side reactions, whereas confined chiral pockets orient substrates for precise transition-state control. Moreover, the modular design of MOFs allows fine-tuning of pore structure and functionality, enabling selective diffusion, cooperative catalysis, and tandem reactions. This perspective outlines strategies for crystallizing chiral molecular catalysts in MOFs and highlights the structural and functional advantages of chiral MOFs (CMOFs) over homogeneous and conventional heterogeneous systems, aiming to inspire innovative CMOF-based catalysts for sustainable synthesis of high-value chemicals and pharmaceuticals. We hope this perspective will deepen readers' understanding of CMOF chemistry and inspire the development of innovative CMOF-based heterogeneous catalysts for the sustainable synthesis of high-value chemicals and pharmaceuticals.
