Chemical Science

Substantial advancements have been achieved in the field of photocatalytic borylation utilizing 4c-7e Lewis base-boryl radicals. However, the utilization of 3c-5e neutral boryl radicals for C–B bond formation remains relatively underexplored due to their inherent instability. In this study, we successfully demonstrated the direct construction of C–B bonds using sodium tetraarylborate as a key reagent. This was accomplished by effectively stabilizing diaryl boryl radicals with nitrile compounds, thereby facilitating the synthesis of valuable boron-containing compounds. Overall, our research elucidates the significant role played by sodium tetraarylborate in enabling an efficient and versatile approach for synthesizing of 1,4,2-diazaborole analogs through a photocatalyzed [3 + 2]-annulation reaction. This mild and adaptable methodology expands synthetic strategies for obtaining diverse derivatives of 1,4,2-diazaboroles, with the RCN–BAr2 complex serving as an effective boron–nitrogen synthon that opens up pathways to multiple boron–nitrogen heterocycles. Furthermore, this breakthrough significantly enhances the applicability of sodium tetraarylborate in photoredox catalysis.

In this study, we explore the potential of the difluoro(trifluoromethoxy)methyl group, CF2–O–CF3, an underexplored but promising structural analog of the trifluoromethoxy group (OCF3). This moiety offers unique electronic properties and enhanced chemical stability due to its multiple C–F bonds, along with the added advantage of C–O bond cleavage, making it an attractive option in fluorine chemistry. We have succeeded in synthesizing difluoro(trifluoromethoxy)methyl compounds via radical amino- and hydroxy-trifluoromethoxylations of β,β-difluorostyrenes. Control experiments, including radical clock experiments, support a free radical mechanism. The synthetic utility of the resulting difluoro(trifluoromethoxy)methyl compounds is also demonstrated through transformations into bioactive analogs, such as pyrrole derivatives, fendiline analogs, and carpropamid analogs, highlighting their potential in drug development.

Perovskite nanocrystals (NCs) with their excellent optical and semiconductor properties have emerged as primary candidates for optoelectronic applications. While extensive research has been conducted on the 3D perovskite phase, the zero-dimensional (0D) form of this promising material in the NC format remains elusive. In this paper, a new synthesis strategy is proposed. According to the Hard–Soft Acid–Base (HSAB) principle, a novel class of hexagonal semiconductor nanocrystals (Cs4PbBr6 HNCs) derived from 0D perovskite Cs4PbBr6 is synthesized by doping an appropriate amount of PbS precursor solution into bromide. These Cs4PbBr6 HNCs are characterized and compared in detail to CsPbBr3 cubic nanocrystals (CsPbBr3 CNCs) as a reference. The Cs4PbBr6 HNCs exhibit significantly enhanced photoluminescence (PL) compared to CsPbBr3 CNCs, with an external quantum efficiency (EQE) reaching 24.19%. Furthermore, they demonstrate superior UV stability compared to CsPbBr3 CNCs. Comparative analysis of their physical properties and morphology, along with detailed investigations into band structures, density of states, and lifetime decay through DFT calculations, is provided. The practical application potential is validated by encapsulating them into backlight LEDs, covering 121.5% and 90.7% of the color gamut of NTSC and Rec. Our research provides comprehensive insights into the photophysical properties of inorganic halide perovskite nanomaterials and explores their potential in the field of optoelectronics.

α-Halo borides are generally constructed via Matteson homologation, and the synthesis of both fluorinated and functionalized ambiphilic boronates is challenging and has received inadequate attention. Herein, we describe the N-methyliminodiacetyl boronate [B(MIDA)]-directed halogenation of alkenes via a complementary sequence involving fluoroalkyl radical addition followed by guided radical-to-metal oxidative addition and C–X reductive elimination. The alkali cation and functional groups in B(MIDA) enable coulombic interaction and weak attraction with halogens, which could weaken the Pd–X bond and assist in C–X bond formation and is verified by DFT calculations. As a result, a wide variety of highly functionalized fluorinated α-halo boronates, including drugs and natural products, are obtained in good or moderate yields through the unique catalytic manifold. Notably, the trifunctionalized (F, X, B) building block could be transformed into diverse modified fluorinated products.

Radical-mediated dearomatization strategies offer a blueprint for building value-added and synthetically valuable three-dimensional skeletons from readily available aromatic starting materials. Herein, we report a novel strategy by leveraging benzene-linked O-oxime esters as triply functionalized precursors to form two distinct persistent radicals under a chemodivergent pathway. These radicals then couple with a cyclohexadienyl radical for either carboamination or carbo-aminoalkylation. Remarkably, a series of 4-(2-aminoethyl)anilines derivatives featuring all-carbon quaternary centers, along with the formation of four different types of chemical bonds, are efficiently constructed through a unique rearomatization cascade in the carboamination. Importantly, employing DMPU as the hydrogen atom transfer (HAT) donor strategically diverts the reaction pathway from the C–N bond formation towards the C–C bond formation. Our mechanistic explorations support a sequential HAT/energy transfer (EnT)/HAT cascade as the key stage for carbo-aminoalkylation involving the N-center iminyl radical. Significantly, this work demonstrates the elegant expansion of divergent C–N and C–C bond formation using the imine moiety within O-oxime esters as the bifunctional reagent, and it broadens the chemical space of both benzenes and O-oxime esters in radical-mediated transformations.

Atomic-scale changes can significantly impact heterogeneous catalysis, yet their atomic mechanisms are challenging to establish using conventional analysis methods. By using identical location scanning transmission electron microscopy (IL-STEM), which provides quantitative information at the single-particle level, we investigated the mechanisms of atomic evolution of Ru nanoclusters during the ammonia decomposition reaction. Nanometre-sized disordered nanoclusters transform into truncated nano-pyramids with stepped edges, leading to increased hydrogen production from ammonia. IL-STEM imaging demonstrated coalescence and Ostwald ripening as mechanisms of nanocluster pyramidalization during the activation stage, with coalescence becoming the primary mechanism under the reaction conditions. Single Ru atoms, a co-product of the catalyst activation, become absorbed by the nano-pyramids, improving their atomic ordering. Ru nano-pyramids with a 2–3 nm² footprint consisting of 3–5 atomic layers, ensure the maximum concentration of active sites necessary for the rate-determining step. Importantly, the growth of truncated pyramids typically does not exceed a footprint of approximately 4 nm² even after 12 hours of the reaction, indicating their high stability and explaining ruthenium's superior activity on nanotextured graphitic carbon compared to other support materials. The structural evolution of nanometer-sized metal clusters with a large fraction of surface atoms is qualitatively different from traditional several-nm nanoparticles, where surface atoms are a minority, and it offers a blueprint for the design of active and sustainable catalysts necessary for hydrogen production from ammonia, which is becoming one of the critical reactions for net-zero technologies.

N-Heterocyclic carbenes (NHCs) have emerged as a privileged ligand family in organometallic chemistry, widely recognized for their unique steric and electronic properties. Among them, the 1,3-bis(2,6-diisopropylphenyl)imidazole-2-ylidene (IPr) ligand has become a cornerstone of NHC chemistry for its remarkable versatility, stability, and broad use. Since its discovery by the Nolan group in 1999, IPr has played a pivotal role in advancing catalytic transformations and facilitating the utilization of NHC ligands in various domains. This article highlights major contributions where IPr has helped shape modern organometallic chemistry, with a focus on its influence in transition metal catalysis and ligand design. Twenty five years after its discovery, the IPr ligand continues to be a benchmark ligand, inspiring and driving innovation.

Solid electrolytes (SEs) are crucial for advancing next-generation rechargeable battery technologies, but their commercial viability is partially limited by expensive precursors, unscalable synthesis, or low ionic conductivity. Lithium tetrahaloaluminates offer an economical option but exhibit low Li⁺ conductivities with high activation energy barriers. This study reports the synthesis of lithium aluminum chalcohalide (Li1.6AlCl3.4S0.6) using inexpensive precursors via one-step mechanochemical milling. The resulting Cl–S mixed-anion sublattice significantly improves the ionic conductivity from 0.008 mS cm⁻¹ for LiAlCl4 to 0.18 mS cm⁻¹ for Li1.6AlCl3.4S0.6 at 25 °C. Structural refinement of the high-resolution XRD patterns and ⁶Li magic-angle-spinning (MAS) NMR quantitative analysis reveals the formation of tetrahedrally-coordinated, face- and edge-shared LiClxSy octahedra that facilitate 3D Li⁺ transport. Ab initio molecular dynamics (AIMD) simulations on Li1.6AlCl3.4S0.6 support an enhanced 3D network for Li⁺ migration with increased diffusivity. All-solid-state battery (ASSB) half-cells using Li1.6AlCl3.4S0.6 exhibit high-rate and long-term stable cycling performance. This work highlights the potential of Li1.6AlCl3.4S0.6 as a cost-effective and high-performance SE for ASSBs.

Recent advancements in 3D structure-based molecular generative models have shown promise in expediting the hit discovery process in drug design. Despite their potential, efficiently generating a focused library of candidate molecules that exhibit both effective interactions and structural diversity at a large scale remains a significant challenge. Moreover, current studies often lack comprehensive comparisons to high-throughput virtual screening methods, resulting in insufficient evaluation of their effectiveness. In this study, we introduce Topology Molecular Type assignment (TopMT-GAN), a novel approach using Generative Adversarial Networks (GANs) for direct structure-based design. TopMT-GAN employs a two-step strategy: constructing 3D molecular topologies within a protein pocket with one GAN, followed by atom and bond type assignment with a second GAN. This integrated approach enables TopMT-GAN to efficiently generate diverse and potent ligands with precise 3D poses for specific protein pockets. When tested on five diverse protein pockets, TopMT-GAN exhibits promising and robust performance, demonstrating a potential enrichment of up to 46 000 fold compared to traditional high-throughput virtual screening methods. This highlights its potential as a powerful tool in early-stage drug discovery, such as hit and lead generation.

Understanding the adsorption behavior of intermediates at interfaces is crucial for various heterogeneous systems, but less attention has been paid to metal species. This study investigates the manipulation of Co³⁺ spin states in ZnCo2O4 spinel oxides and establishes their impact on metal ion adsorption. Using electrochemical sensing as a metric, we reveal a quasi-linear relationship between the adsorption affinity of metal ions and the high-spin state fraction of Co³⁺ sites. Increasing the high-spin state of Co³⁺ shifts its d-band center downward relative to the Fermi level, thereby weakening metal ion adsorption and enhancing sensing performance. These findings demonstrate a spin-state-dependent mechanism for optimizing interactions with various metal species, including Cu²⁺, Cd²⁺, and Pb²⁺. This work provides new insights into the physicochemical determinants of metal ion adsorption, paving the way for advanced sensing technologies and beyond.

The layer-stacking mode of a two-dimensional (2D) material plays a dominant role either in its topology or properties, but remains challenging to control. Herein, we developed alkali-metal ion-regulating synthetic control on the stacking structure of a vinylene-linked covalent triazine framework (termed sp²c-CTF) for improving hydrogen peroxide (H2O2) photoproduction. Upon the catalysis of EtONa in Knoevenagel polycondensation, a typical eclipsed stacking mode (sp²c-CTF-4@AA) was built, while a staggered one (sp²c-CTF-4@AB) was constructed using LiOH. The AB stacking might be induced by the Li⁺ promoted Lewis acid–base interactions with the nitrogen atoms of s-triazine units which would endow the s-triazine units with a charged state and enlarge the total crystal stacking energy. Specifically, the shift in the stacking mode speeds up electron transfer within each layer and along interlayers, thereby improving the photocatalytic activity. sp²c-CTF-4@AB features superior activity over the eclipsed stacking counterpart (sp²c-CTF-4@AA) in sacrificial agent-free H2O2 generation, comparable to the state-of-the-art COF photocatalysts, which has not been demonstrated in this field before. This work demonstrates that regulating the interlayer-stacking mode of COFs can endow them with high photocatalytic activity, further inspiring the development of heterogeneous catalysis.

Poly(ethylene oxide) (PEO)-based solid-state polymer electrolyte (SPE) is a promising candidate for the next generation of safer lithium-metal batteries. However, the serious side reaction between PEO and lithium metal and the uneven deposition of lithium ions lead to the growth of lithium dendrites and the rapid decline of battery cycle life. Building a LiF-rich solid electrolyte interface (SEI) layer is considered to be an effective means to solve the above problems. Here, porous organic polymers (POPs) with aromatic structures and non-aromatic structures were synthesized and introduced into the PEO-based SPE as fillers to explore the effect of aromatic structures on LiF-rich SEI formation. The results show that the POPs containing aromatic groups could catalyze the decomposition of LiTFSI to form a stable LiF-rich SEI layer and inhibit the growth of lithium dendrites. The discharge capacity of the LFP/Li battery is 103 mA h g⁻¹ after 500 cycles at 1C (100 °C). It provides a promising way to improve the stability of the solid electrolyte matrix and SEI layer.

Two-dimensional conductive metal–organic frameworks (2D c-MOFs) with high electrical conductivity and tunable structures hold significant promise for applications in metal-ion batteries. However, the construction of 3D interpenetrated c-MOFs for applications in metal-ion batteries is rarely reported. Herein, a 3D four-fold interpenetrated c-MOF (Cu-DBC) constructed by conjugated and contorted dibenzo[g,p]chrysene-2,3,6,7,10,11,14,15-octaol (DBC) ligands is explored as an advanced cathode material for sodium-ion batteries (SIBs) for the first time. Notably, the expanded conjugated and four-fold interpenetrating structure endows Cu-DBC with transmission channels for electrons and sufficient spacing for sodium ion diffusion. As expected, the Cu-DBC cathode showcases higher specific capacity (120.6 mA h g⁻¹, 0.05 A g⁻¹) and robust cycling stability (18.1% capacity fade after 4000 cycles, 2 A g⁻¹). Impressively, the Cu-DBC cathode also exhibits good electrochemical properties at extreme temperatures (−20 °C and 50 °C). A series of in/ex situ characterizations and systematic theoretical calculations further reveal the sodium-ion storage mechanism of Cu-DBC, highlighting a three-electron redox process on the redox-active [CuO4] units. This work provides valuable insights for exploring and enriching the applications of 3D interpenetrated c-MOFs in metal-ion batteries.

Controlling symmetrical or asymmetrical growth has allowed a series of novel nanomaterials with prominent physicochemical properties to be produced. However, precise and continuous size growth based on a preserved template has long been a challenging pursuit, yet little has been achieved in terms of manipulation at the atomic level. Here, a correlated silver cluster series has been established, enabling atomically precise manipulation of symmetrical and asymmetrical surface structure expansions of metal nanoclusters. Specifically, the C3-axisymmetric Ag29(BDTA)12(PPh3)4 nanocluster underwent symmetrical and asymmetrical surface structure expansions via an acid-mediated synthetic procedure, giving rise to C3-axisymmetric Ag32(BDTA)12(PPh3)10 and C1-axisymmetric Ag33(BDTA)12(PPh3)11, respectively. In addition, structural transformations, including structural degradation from Ag32 to Ag29 and asymmetrical structural expansion from Ag32 to Ag33, were rationalized theoretically. More importantly, the asymmetrically structured Ag33 nanoclusters followed a chiral crystallization mode, and their crystals displayed high optical activity, derived from CD and CPL characterization. This work not only provides an important model for unlocking the symmetrical/asymmetrical size growth mechanism at the atomic level but also pioneers a promising approach to activate the optical activity of cluster-based nanomaterials.

Silicon (Si) is considered a promising anode material for next-generation lithium-ion batteries due to its high theoretical specific capacity and earth-abundancy. However, challenges such as significant volume expansion, unstable solid electrolyte interphase (SEI) formation in incompatible electrolytes, and slow lithium-ion transport lead to its poor cycling and rate performance. In this work, it is demonstrated that superior cyclability and rate capability of Si anodes can be achieved using ethyl fluoroacetate (EFA) and fluoroethylene carbonate (FEC) solvents with low binding energy with Li⁺ but with sufficiently high relative dielectric constants. By weakening the interaction between Li⁺ and the solvent, the energy barrier for the Li⁺ desolvation process is lowered, while ensuring the conductivity and diffusion of Li⁺. As a result, the silicon–carbon anode with the optimized electrolyte exhibits excellent cycling and rate performance, and can work reversibly with a high capacity of 1709.1 mAh g⁻¹ that proceeds for over 250 cycles and retains 85.2% of its capacity at 0.2C. Furthermore, the Si/C‖LiFePO4 (LFP) full cell shows an extended service life of more than 500 cycles. This work offers valuable insights into the design of weakly solvating electrolytes for high-performance Si-based batteries.

Correction for ‘Radical ligand transfer: mechanism and reactivity governed by three-component thermodynamics’ by Zuzanna Wojdyla et al., Chem. Sci., 2024, 15, 8459–8471, https://doi.org/10.1039/D4SC01507J.

Despite the evident demand and promising potential of disulfide-functionalized amino acids and peptides in linker chemistry and peptide drug discovery, those disulfurated specifically at the α-position constitute a unique yet rather highly underexplored chemical space. In this study, we have developed a method for preparing SS-linked amino acid/peptide derivatives through a base-catalyzed disulfuration reaction of azlactones, followed by the ring-opening functionalization. The disulfuration reaction proceeds under mild conditions, yielding disulfurated azlactones in excellent yields across a variety of N-dithiophthalimides and diverse azlactones derived from various amino acids and peptides. Leveraging the ready availability of N-dithiophthalimides from several bilateral disulfurating reagents, this method allows for the modular integration of functional molecules and azlactones into SS-linkage in two-step operations. Furthermore, due to the transformability of the azlactone moiety through ring-opening with various nucleophiles, our method provides a wide variety of functional molecule-tagged amino acids and oligopeptides bearing SS-linkages in a modular and time-efficient manner, serving as a valuable tool for linker chemistry and peptide chemistry.

We report a series of dibenzyl isophthalates (DBIs) as novel hosts for room-temperature phosphorescence (RTP) host–guest systems, achieving RTP quantum yields (QY) of up to 77% or lifetimes of up to 21.0 s with the guest coronene-d12. Furthermore, a 4,4′-Br substituted DBI was used to form host–guest RTP systems with 15 different aromatic guest molecules, to tune the phosphorescence emission color from blue to red and to demonstrate the versatility of the host. Mechanistic insights were gained through a host–guest–matrix system which shows RTP by trace combinations of a 4,4′-Br DBI host (0.10 wt%) and a pyrene-d10 guest (0.01 wt%) in an otherwise non-RTP-emissive aromatic matrix. This work establishes DBIs as readily available and versatile, tunable hosts for RTP host–guest systems, posing an alternative to polymeric hosts.

In this article, we highlight the recent report of Greb et al. on the use of a structurally constrained P–P bonded system for phosphinophosphination of alkenes, alkynes, and carbonyls with high regio- and stereoselectivity (https://doi.org/10.1039/D4SC06581F).

Thermoelectric technology plays an important role in developing sustainable clean energy and reducing carbon emissions, offering new opportunities to alleviate current energy and environmental crises. Nowadays, GeTe has emerged as a highly promising thermoelectric candidate for mid-temperature applications, due to its remarkable thermoelectric figure of merit (ZT) of 2.7. This review presents a thorough overview of the advancements in GeTe thermoelectric materials, meticulously detailing the crystal structure, chemical bonding characteristics, band structure, and phonon dynamics to elucidate the underlying mechanisms that contribute to their exceptional performance. Moreover, the phase transition in GeTe introduces unique degrees of freedom that enable multiple pathways for property optimization. In terms of electrical properties, noticeable enhancement can be realized through strategies such as band structure modulation, carrier concentration engineering, and vacancy engineering. For phonon transport properties, by incorporating defect structures with varying dimensions and constructing multi-scale hierarchical architectures, phonons can be effectively scattered across different wavelengths. Additionally, we provide a summary of current research on devices and modules of GeTe. This review encapsulates historical progress while projecting future development trends that will facilitate the practical application of GeTe in alignment with environmentally sustainable objectives.

Many protein bioconjugation strategies focus on the modification of lysine residues owing to the nucleophilicity of their amine side-chain, the generally high abundance of lysine residues on a protein's surface and the ability to form robustly stable amide-based bioconjugates. However, the plethora of solvent accessible lysine residues, which often have similar reactivity, is a key inherent issue when searching for regioselectivity and/or controlled loading of an entity. A relevant example is the modification of antibodies and/or antibody fragments, whose conjugates offer potential for a wide variety of applications. Thus, research in this area for the controlled loading of an entity via reaction with lysine residues is of high importance. In this article, we present an approach to achieve this by exploiting the quantitative and reversible site-selective modification of disulfides using pyridazinediones, which facilitates near-quantitative proximity-induced reactions with lysines to enable controlled loading of an entity. The strategy was appraised on several clinically relevant antibody fragments and enabled the formation of mono-labelled lysine-modified antibody fragment conjugates via the formation of stable amide bonds and the use of click chemistry for modular modification. Furthermore, through the use of multiple cycles of this novel strategy, an orthogonally bis-labelled lysine-modified antibody fragment conjugate was also furnished.

The direct transformation of methane into C2 oxygenates such as acetic acid selectively using molecular oxygen (O2) is a significant challenge due to the chemical inertness of methane, the difficulty of methane C–H bond activation/C–C bond coupling and the thermodynamically favored over-oxidation. In this study, we have successfully developed a porous aluminium metal–organic framework (MOF)-supported single-site mono-copper(ii) hydroxyl catalyst [MIL-53(Al)-Cu(OH)], which is efficient in directly oxidizing methane to acetic acid in water at 175 °C with a remarkable selectivity using only O2. This heterogeneous catalyst achieved an exceptional acetic acid productivity of 11 796 mmolCH3CO2H molCu⁻¹ h⁻¹ in 9.3% methane conversion with 95% selectivity in the liquid phase and can be reused at least 6 times. Our experiments, along with computational studies and spectroscopic analyses, suggest a catalytic cycle involving the formation of a methyl radical (˙CH3). The confinement of Cu-active sites within the porous MIL-53(Al) MOF facilitates C–C bond coupling, resulting in the efficient formation of acetic acid with excellent selectivity due to the internal mass transfer limitations. This work advances the development of efficient and chemoselective earth-abundant metal catalysts using MOFs for the direct transformation of methane into value-added products under mild and eco-friendly conditions.

This manuscript describes a strategy to readily access diverse aryl and homoaryl alanine-containing pharmaceutically relevant macrocyclic peptides. A two-step sequence involving the late-stage installation of the pyridinium functionality on macrocyclic peptides followed by reductive couplings was implemented. These transformations are amenable to microscale high-throughput experimentation (HTE) and enable rapid access to aryl alanine-containing macrocyclic peptides that would otherwise be inaccessible via solid-phase peptide synthesis using commercially available amino acids. Numerous aryl and heteroaryl derivatives can be effectively used in these reactions. In addition, a systematic investigation was undertaken using an “informer” set of macrocyclic peptides which revealed the compatibility of the late-stage diversification with peptides containing diverse side chain functionalities.

Alzheimer's disease (AD) is the most prevalent neurodegenerative dementia, marked by progressive cognitive decline and memory impairment. Despite advances in therapeutic research, single-target-directed treatments often fall short in addressing the complex, multifactorial nature of AD. This arises from various pathological features, including amyloid-β (Aβ) aggregate deposition, metal ion dysregulation, oxidative stress, impaired neurotransmission, neuroinflammation, mitochondrial dysfunction, and neuronal cell death. This review illustrates their interrelationships, with a particular emphasis on the interplay among Aβ, metal ions, and AD-related enzymes, such as β-site amyloid precursor protein cleaving enzyme 1 (BACE1), matrix metalloproteinase 9 (MMP9), lysyl oxidase-like 2 (LOXL2), acetylcholinesterase (AChE), and monoamine oxidase B (MAOB). We further underscore the potential of therapeutic strategies that simultaneously inhibit Aβ aggregation and address other pathogenic mechanisms. These approaches offer a more comprehensive and effective method for combating AD, overcoming the limitations of conventional therapies.

Correction for ‘Reconstructing the phase of vanadium oxides enables redox-catalysis manipulated reversible sulfur conversion for stable Zn–S batteries’ by Hao Luo et al., Chem. Sci., 2025, https://doi.org/10.1039/d4sc06593j.