Chemical Reviews最新文献

Transition metal complexes featuring unusual oxidation states represent an exciting frontier in inorganic chemistry. This review surveys the unusual oxidation states of two biologically important metals, platinum (Pt^I and Pt^III) and gold (Au^II), examining their electronic structures, bonding characteristics, and biomedical relevance, among other features. Emphasis is placed on synthetic strategies, redox behavior, and factors influencing their stability and stabilization. Pt^III complexes can potentially offer an alternative to the traditional Pt^II/IV anticancer chemotherapy framework and be an intermediate in Pt^II/IV redox chemistry. Indeed, the Pt^III-based platinum blues have been widely investigated as anticancer agents soon after the landmark discovery of cisplatin as a cancer chemotherapeutic. Au^II complexes are less explored for their biological properties but may be intermediates in Au^I/III redox chemistry and offer an alternative pathway to gold-based chemotherapeutics. We outline current challenges and future directions in this evolving field, where fundamental chemistry meets therapeutic innovation.

High-energy-density all-solid-state lithium batteries (ASSLBs) require cathodes with exceptional mechanical integrity, interfacial compatibility, and long-term electrochemical stability. Single-crystal (SC) layered oxides, distinguished from polycrystalline (PC) counterparts by their grain-boundary-free architecture and crystallographic uniformity, exhibit enhanced structural and interfacial stability while providing an ideal model system for decoupling electro-chemo-mechanical interactions. These characteristics enable precise investigation of facet-dependent transport, reaction kinetics, and degradation pathways─insights that can inform the design of both SC and advanced PC cathodes. In this review, we examine the anisotropic lithium transport, mechanical responses, and interfacial behaviors of SC cathodes, and compare them systematically with PCs to clarify how microstructural differences influence performance in ASSLBs. We further summarize advances in intrinsic material optimization, interfacial engineering, and composite electrode architectures, alongside state-of-the-art characterization and modeling tools for probing degradation mechanisms and coupling effects. Finally, we outline key challenges and research directions to accelerate the practical deployment of SC cathodes in next-generation high-energy-density ASSLBs.

Ionic liquids (ILs) have emerged as highly tunable sorbents and membranes for gas separation, especially in the purification of CO₂-containing gas streams such as air, natural gas, biogas, and syngas. Their negligible volatility, high thermal stability, and chemical versatility position them as promising alternatives to conventional amine and alkaline metal derivative-based systems, effectively addressing key challenges such as volatility, stability, and high regeneration energy. This Review explores IL-derived systems for CO₂-related gas separation across dense, porous, and supported categories. At the dense liquid level, we discuss strategies for tailoring IL properties to optimize CO₂ sorption, focusing on the correlation between IL-CO₂ interaction strength, uptake capacity, and regeneration energy. Key advancements in carbon capture, including amino-functionalized (AILs) and superbase-derived ILs (SILs), are highlighted, along with strategies such as chemical structure engineering, multiple binding site integration, alternative driving force exploration, and stability enhancement. Then, the porous liquids (PLs) scale focuses on the emerging field integrating IL properties with permanent porosity engineering, spanning ultramicropores (<5 Å) to macropores (around 100 nm). These innovations improve gas uptake capacity, accelerate transport kinetics, introduce the gating effect, and enable the coexistence of active sites with antagonistic properties within a single IL medium. At the supported IL scale, the discussion shifts to IL- and ionic pair-modified sorbents and membranes, emphasizing the modulation of cations and anions, confinement effects from porous supports, and the IL–interface interaction to enhance CO₂ separation performance, particularly in diluted gas streams. Beyond separation, this Review highlights IL-based integrated processes for CO₂ capture and conversion into value-added chemicals via thermocatalytic, electrocatalytic, and photocatalytic pathways. At each scale, advanced computational and experimental tools for IL design are also discussed, providing insights into stability enhancement, sorption efficiency, and process integration. The Review concludes by addressing existing challenges and outlining future directions for IL-driven innovations in gas separation technologies.

Photon upconversion, the process of converting low-energy photons to higher energy ones, shows promise for applications in solar energy, photocatalysis, biomedicine, and additive manufacturing. In triplet–triplet annihilation (TTA), incident low-energy photons populate metastable spin-triplet states that annihilate to generate high-energy emissive spin-singlet states. Thus, TTA-based photon upconversion (TTA-UC) can operate efficiently under incoherent and low-intensity excitation, such as sunlight. In this Review, we discuss the recent emergence of halide perovskite-based materials as potent triplet sensitizers for a variety of applications. Due to their strong and tunable absorption and high defect tolerance, perovskite materials ranging from nanocrystalline to bulk semiconductors enable efficient TTA-UC in both solution and solid-state systems. After introducing the TTA-UC process and giving a brief overview of its beginnings, we first consider TTA-UC systems based on perovskite nanocrystals and low-dimensional perovskite-inspired materials and the achievements that have been made in those areas. We then focus on the mechanism of bulk perovskite-sensitized TTA-UC, the impact the underlying structure holds, and review the current challenges in perovskite-sensitized solid-state UC and outline future research directions to unlock the full potential of TTA-UC in practical applications.

This review chronicles rapid advances in computational approaches in high-energy-density materials (HEDMs), which display a tradeoff between performance and safety that poses challenges from molecular to system levels. We illustrate the transformative fusion of predictive theory and modern experimentation─which is driving the transition of HEDM science from empirical discovery to data-driven rational design. The analysis begins with the physics-based foundation of the field, illustrating how quantum chemistry and multiscale dynamics provide insight into stability and emergent behavior from an energetic perspective. At the heart of our analysis lies the iterative feedback loop between simulation and experimental validation, a core element of this emerging paradigm. The review ultimately frames the critical questions and opportunities that will define the future of the field, as we move toward a new generation of HEDMs that are potentially safer, more sustainable, and higher-performing energetic materials.

Vicinal amino alcohols, also called 1,2- or β-amino alcohols, are an important class of chemical modalities that may serve as chiral ligands for metal-based catalysts or as catalysts themselves and are found within numerous pharmaceutically active compounds. As such, a multitude of strategies have been adopted for their preparation, with traditional approaches leveraging diastereoselective synthesis of this scaffold based upon existing stereochemistry within a substrate. Many times, naturally occurring chiral variants or syntheses of the moiety from chiral natural sources have been utilized. Given their prominence, there have been myriad strategies developed for the catalytic enantioselective synthesis of β-amino alcohols; however, these have largely focused on the formation of secondary alcohols. In this Review, we detail the existing methods in the significantly less explored area of the catalytic enantioselective preparation of 1,2-amino tertiary alcohols and their analogues.

Stretchable ionic conductors (SICs) have been the focus of recent research due to their potential in soft electronics, bioelectronics, and flexible energy devices. A key challenge in this field is achieving a good balance between ionic conductivity and mechanical robustness, particularly in solvent-free systems where durability and long-term stability are critical. Recent progress in elastomer-based SICs has demonstrated innovative strategies to enhance performance, including the use of dynamic cross-linking, supramolecular interactions, and phase-separated networks. Materials such as poly(ionic liquid)-based elastomers (PILs), polymerizable deep eutectic solvents (PDESs), and dual-network ionogels have emerged as promising candidates, offering high stretchability, tunable conductivity, and improved mechanical strength. This review provides an overview of the design strategies and key properties of SICs, focusing on the interplay between mechanical performance and ion-transport. By analyzing recent advances in material architecture, cross-linking chemistry, and ion transport mechanisms, we highlight promising approaches for optimizing SICs for the next generation of stretchable devices.

Reversible chemistry strategies in cancer treatment and diagnosis have attracted significant attention due to their unique ability to dynamically respond to both exogenous (e.g., light, ultrasound, and magnetic fields) and endogenous (e.g., pH, redox potential, and hypoxia-normoxia) stimuli, thereby modulating the functional characteristics of materials. Reversible cancer therapy offers distinct advantages over irreversible cancer therapy including sustainable cyclic function, shape-specific function, tumor-site-specific function, tumor-specific targeting, on-demand control, deep tumor penetration, and long-term circulation and drug retention. This review comprehensively explores reversible chemistry strategies for cancer therapy and imaging, providing a comprehensive overview of utilizing multiscale (molecular-scale, nanoscale, microscale, and macroscale) materials for various reversible control mechanisms, such as electronic transitions, molecular isomerization, valence state changes, material morphology changes, and mechanical motion. Furthermore, we present various applications, advantages, and challenges of reversible chemistry in cancer therapy and imaging along with the potential for clinical applications and associated challenges. In conclusion, reversible therapeutic and diagnostic approaches offer promising avenues for precise cancer treatment and early diagnosis.

During the past decade, the advancement and approval of novel radiopharmaceuticals for clinical application has led to a resurgence of the field of radiochemistry and specifically the coordination chemistry of radionuclides. In addition to well established radionuclides, short-lived radioisotopes of other elements are becoming accessible using new isotope production methods, necessitating the development of coordination chemistry compatible with the aqueous chemistry of such elements under tracer level conditions. As radiochemistry with radioactive metal ions relevant for radiopharmaceuticals is conducted at the nano- to picomole scale, conventional chemical characterization techniques can generally not be applied. Therefore, careful consideration and interfacing of tracer-level compatible techniques and macroscopic characterization methods is required. This Review provides an in-depth survey of common, contemporary characterization strategies for the coordination chemistry of radionuclides, including case studies to demonstrate context and relevance for the prospective development of clinically translatable radiopharmaceuticals.

Soft materials are polymer networks that can be easily deformed by external forces. Incorporating dynamic bonds into these networks imparts various functionalities─such as self-healing, recyclability, and 3D printability─by enabling fast and reversible bond formation. However, the relatively short lifetimes of dynamic bonds compared with permanent covalent bonds can compromise the mechanical robustness of the material. This review highlights design strategies that harness dynamic bonds effectively to achieve both functionality and mechanical robustness in soft materials. We first survey the types of dynamic bonds and their characteristic lifetimes, followed by introducing analytical methods to quantify the network dynamicity. Since the required degree of dynamicity varies depending on the target functionality, we further discuss how to incorporate appropriate dynamic bonds for functionality. Through this, we aim to provide design guidelines for soft materials that combine functionalities with mechanical toughness for reliable use in advanced applications.