Chemical Society Reviews最新文献

Molecular nanographenes (NGs)—graphene analogues at the nanoscale—exhibit atomically defined monodispersity in both size and shape. This synthetic precision enables fine control over their properties. Among the emerging strategies to modulate their electronic and optical properties, vertical π–π stacking between the graphitized layers has recently gained attention as a powerful design tool. In this review, we explore the synthesis, structural features, and functional implications of bilayer and multilayer nanographenes, with a particular focus on the bilayer effect—a through-space electronic communication arising from the interlayer overlap. We discuss how the degree of π–π overlap, rather than solely π-extension, governs key properties such as HOMO–LUMO gap, redox behavior, photoluminescence shifts and quatum yields, and chiroptical responses. Molecular architectures incorporating helicenes, spirocycles, or non-benzenoid motifs enable the deviation from planarity, ususally presented in nanographenes, allowing the precise synthesis of covalently π–π stacked topologies that amplify this effect. Furthermore, this concept also extends to other NGs such as multilayers, supramolecular assemblies, and donor–acceptor complexes, revealing the versatility of the bilayer approach. The first synthetic approaches to access enantiomerically pure bilayer NGs are also disclosed, opening new avenues for their use in advanced technological applications. Overall, the bilayer effect emerges as a novel structural parameter for tuning the properties and function of π-conjugated carbon-based materials, opening new frontiers in molecular chiral optoelectronics, spintronics, and quantum nanoscience.

Correction for ‘Supported metal nanoparticles on porous materials. Methods and applications’ by Robin J. White et al., Chem. Soc. Rev., 2009, 38, 481–494, https://doi.org/10.1039/B802654H.

Photothermal dry reforming of methane (PT-DRM) presents a promising strategy for simultaneously mitigating greenhouse gas emissions and valorizing carbon resources by converting CH₄ and CO₂ into syngas under solar irradiation. By integrating photonic and thermal activation, this hybrid catalytic approach addresses the kinetic and thermodynamic limitations of conventional DRM, enabling efficient activation of chemically inert molecules through mechanisms such as localized surface plasmon resonance, semiconductor bandgap excitation, and interfacial charge transfer. This review provides a comprehensive analysis of PT-DRM catalyst architectures, which are systematically categorized into nanoparticle-based catalysts, fully exposed active site systems, and hybrid nanostructures. We highlight how variations in morphology, dispersion, and electronic configuration govern light–heat synergy, intermediate evolution, and suppression of side reactions. Moreover, we dissect the mechanistic pathways involved, including lattice oxygen cycling, oxygen vacancy dynamics, and dual-site redox mechanisms, with emphasis on how these pathways diverge across structural motifs and reaction environments. Despite these advances, several unresolved challenges persist, such as the difficulty in decoupling photonic and thermal effects, the instability of active sites under operando conditions, the suppression of side reactions, and the lack of real-time diagnostic tools to probe nanoscale thermal gradients and intermediate transformations. By bridging structure–activity relationships with photophysical and interfacial phenomena, this review aims to guide the rational design of next-generation PT-DRM catalysts and accelerate the development of solar-driven syngas production technologies.

The composition of halide perovskite has rapidly changed from methylammonium lead triiodide (MAPbI₃) to formamidinium lead triiodide (FAPbI₃) to achieve high-performance solar cells with power conversion efficiencies of over 27%. FAPbI₃ is well known for its suitable bandgap, closer to the ideal one, and improved stability under external stress. Nevertheless, the role of FA⁺ in determining the outstanding optoelectronic properties of FAPbI₃, distinct from MAPbI₃, is relatively less understood. In this review, the interaction between FA⁺ and PbI₆⁴⁻ octahedral frameworks is investigated in comparison with MA⁺, which readily affects the chemical bonding nature of the inorganic framework and thus determines the optoelectronic properties and structural stability. Closely related to the fundamental understanding of FAPbI₃, the progress of FAPbI₃-based perovskite solar cells is discussed from a strategic point of view to resolve their metastable character and surface defect properties to provide insights into future research directions.

Ammonia (NH₃), one of the world's most vital chemicals and energy carriers, has attracted wide attention. Currently, NH₃ is mainly produced using the traditional, energy-intensive Haber–Bosch (H–B) technology, which has a large impact on the environment. Therefore, developing a low-cost, high-efficiency, and eco-friendly way to produce NH₃ is highly desirable. Photo-, electro-, photoelectro-, and alkali–metal-mediated catalytic reactions powered by renewable and clean energy under ambient conditions offer alternatives to the H–B process and have recently gained significant interest. However, efficient nitrogen reduction is a key requirement, limiting the selectivity and activity for the green synthesis of NH₃ because the N₂ activation process in a green catalytic system is difficult to complete due to its thermodynamic instability and chemical inertness. Compared to the reduction of N₂, the catalytic reduction of some soluble and harmful high-valent sources (e.g., NO, NO₂⁻, and NO₃⁻) is considered an effective method for increasing NH₃ synthesis efficiency. This review article focuses on the important features of the green catalytic conversion of multiple nitrogen resources into NH₃ by summarizing the fundamental mechanistic understanding, catalytic descriptors, and current advances, along with the various catalysts used for these conversion strategies and their structure–activity relationships. Meanwhile, opportunities and prospects for reactor design and construction for potential NH₃ production at high current densities are also discussed, focusing on achieving a high yield rate, Faraday efficiency, and energy efficiency. This will provide valuable guidance for constructing catalysts and optimizing reaction systems that can meet the needs of practical applications.

Nitriles, as valuable compounds characterized by carbon–nitrogen triple bonds, represent an important class of synthons in organic synthetic chemistry and materials science. Over the past two decades, the conversion of nitriles to diverse N-heterocycles has attracted significant attention among chemists, owing to its numerous synthetic and economic advantages. Three main types of reactions involving nitriles in N-heterocycle synthesis have been reported, including nucleophilic addition, electrophilic addition and radical addition reactions. In this review, a comprehensive overview of recent progress in nitrile cyclization chemistry is presented. This review is organized and discussed based on the transition metal-catalyzed and metal-free induced N-heterocycle synthesis by C–C, C–N and N–N bond formation reactions using nitriles as nitrogen sources, with an emphasis on the reaction development, mechanisms and subsequent applications of these reactions.

Aromatic Azo molecules, including azobenzenes (Ph–NN–Ph) and heteroaryl Azo (Het–NN–Ph or Het–NN–Het), have emerged as versatile and high-performing photoactive switches for biomedical applications. Despite decades of extensive research on aromatic Azo as molecular photoswitches, the full translational potential of these small molecules remains underexploited. This review systematically outlines structural design strategies for aromatic Azo, spanning from functional substituent engineering to π-conjugation modulation, to fine-tune its photophysical properties. We summarize state-of-the-art synthetic methodologies for crafting multifunctional aromatic Azo frameworks, contrast the distinct isomerization mechanisms of azobenzenes versus heteroaryl Azo derivatives, and highlight the latest biomedical application advances, including biological imaging and detection, drug delivery, photopharmacology, phototherapy, miscellanea photo responsive biomaterials and constructs, and control in chemical biology. Furthermore, we discuss clinical translation challenges and opportunities in this field, proposing innovative strategies to address critical issues. This review aims to substantially advance the burgeoning field of aromatic Azo photoactive small molecules for biomedical applications.

Radical retrosynthesis has emerged as a powerful strategy for the modern assembly of complex natural products, offering a one-electron logic that complements traditional polar disconnections. This review highlights recent advances—particularly developed over the past decade—in radical methodologies and their strategic applications in the total synthesis of terpenoid natural products. Emphasis is placed on how various radical precursors, including alkenes, carboxylic acids, halides, alcohols, carbonyl compounds, and alkanes, have been transformed through innovative processes such as photoredox catalysis, metal–hydride hydrogen atom transfer (MHAT), redox-active ester (RAE) chemistry, cross-electrophile couplings (XEC), and HAT-based C–H functionalization. By organizing the discussion around precursor classes and corresponding reaction modes, we illustrate how radical-based synthetic strategies enable efficient construction of quaternary stereocenters and modular assembly of complex polycyclic scaffolds.

Sulfenylcarbenes and sulfenylnitrenes are ambiphilic intermediates possessing an unoxidized sulfur atom adjacent to their reactive center. Their unique properties and tunable reactivity make them a model species for studying carbenes and nitrenes in cycloaddition reactions, atom incorporation, late-stage functionalizations, among other applications. They have gained significant attention recently and hold considerable promise for novel reaction development and discovery. Herein, we analyze the chemistry of sulfenylcarbenes and sulfenylnitrenes, emphasizing their generation and applications in contemporary organic synthesis.

The need for selective and efficient anticancer therapies drives the development of gold N-heterocyclic carbene (NHC) as efficient metallodrugs. Their stability, tunable electronics, and versatile steric features make NHCs ideal ligands, which, paired with an antiproliferating gold centre, form an exemplary metal complex for anticancer research. This review highlights the progress made in designing gold NHC complexes, emphasizing strategies to enhance cytotoxicity and selectivity towards cancer cells while minimizing toxicity to healthy tissues, emphasizing the crucial role of the NHC ligand. Furthermore, challenges concerning revealing the precise modes of action are discussed. Mechanistic pathways beyond the inhibition of thioredoxin reductase are highlighted. By underlining recent developments, this review aims to pave the way to a rational design of next-generation gold NHC complexes.