Cyclic boronic hemiesters, boron isosteres of lactones, display unique and valuable chemical properties. Herein, we report a novel method for their synthesis via nickel-catalyzed decarbonylative borylation, enabled by electron-rich phosphine ligands to achieve a formal “C-to-B” atom swap. This strategy efficiently transforms a variety of coumarin derivatives and seven-membered dibenzolactones into the corresponding benzoxaborines, showcasing broad functional group tolerance and synthetic versatility.

We report a carbon-to-boron “C-to-B” atom swap reaction to transform readily available coumarins into their isosteric benzoxaborins via a net replacement of the C═O group with a B─OH moiety. These conditions were applied to coumarin natural products and other 6–7-membered lactones (25 examples, 29%–93%). We leverage this methodology to transform a flat polyaromatic hydrocarbon into three-dimensional tribenzo[b.d.f]oxepines through a series of atom-swapping reactions followed by ring expansion via the oxaborin intermediate.

A metalloenzyme-catalyzed asymmetric transfer hydrogenation platform has been developed for the stereoselective synthesis of chiral amines. In contrast to natural NAD(P)H-dependent C═N bond reductases, this strategy employs carbonic anhydrase or P450 as a catalyst in combination with a silane-reducing agent, offering a fully orthogonal alternative to conventional NAD(P)H-dependent cellular processes.

Chiral amines are prevalent in natural products, pharmaceuticals, and organic catalysts. Their increasing demand has driven the advancement of synthetic methods. In this study, we developed a metalloenzyme-catalyzed asymmetric transfer hydrogenation method for the synthesis of chiral amines. Given the challenges of traditional chemical synthesis, which relies on precious metals and complex synthetic ligands, our approach utilizes base metals derived from natural metalloenzymes for transfer hydrogenation and employs protein scaffolds to achieve stereochemical control. Furthermore, in contrast to natural NAD(P)H-dependent C═N bond reductases, this strategy utilizes silanes as reducing agents and is entirely orthogonal to conventional NAD(P)H-dependent cellular functions. This reactivity highlights the potential to develop new-to-nature enzymatic functions capable of addressing challenges in both organic synthesis and biosynthesis.

Mo 4d orbital hybridized with the Se 4p-Pb 6p to provide conduction band convergence, and PbSe-MoSe2 modular nanostructures lead to high thermoelectric performance in MoCl5 doped n-type PbSe.

n-type lead chalcogenides showing high thermoelectric performance are rare due to the larger energy offset between the two lowest energy conduction bands minima, leaving ample opportunity to modulate electronic structure for improving their thermoelectric performance. Here, we present a remarkable thermoelectric figure of merit (zT) of ∼1.8 at 873 K in n-type PbSe doped with MoCl5 by modulation of the conduction bands, while simultaneously suppressing the phonon transport. Doping MoCl5 in PbSe induces notable convergence of conduction bands and an increased density of states near the Fermi level, mainly due to the contribution of Mo 4d orbital hybridized with the Se 4p-Pb 6p. This results in an improved Seebeck coefficient, despite maintaining a high n-type charge carrier concentration resulting in an excellent power factor (σS2) of ∼21 µW cm−1 K−2 at 873 K for PbSe + 1 mol% MoCl5. When the solid solution limit of the doping exceeds, it forms unique modular nano-heterostructures (5-30 nm) of PbSe-MoSe2 misfit layered compounds embedded in PbSe matrix. These nano-heterostructures significantly intensify phonon scattering, leading to an ultralow lattice thermal conductivity (κlat) of 0.20 W m−1 K−1 at ∼725 K in PbSe + 1 mol% MoCl5 sample.

We present the innovative design and construction of a synergistic covalently and mechanically interlocked polymer (CMIP), in which the covalent polymer (CP) and the mechanically interlocked polymer (MIP) are seamlessly integrated into a unified system. This design effectively overcomes the inherent limitations of traditional polymer networks, establishing a new paradigm in the field of novel materials design.

Integrating different polymer types into a unified system in a thoughtful manner leverages their complementary advantages, providing a promising strategy for developing high-performance materials. Mechanically interlocked polymers (MIPs), characterized by their unique spatial entanglement, exhibit distinctive performance advantages, yet their potential to expand material properties through rational integration with other polymer architectures presents substantial opportunities for continued investigation. Herein, we report a coherent integration of covalent polymers (CPs) and mechanically interlocked polymers through sequential orthogonal polymerizations, developing a novel synergistic covalently and mechanically interlocked polymer (CMIP) featuring both structural stability and force-induced dynamics. Compared to its structurally similar but noninterlocked control sample, CMIP demonstrates markedly enhanced thermomechanical stability and performance recovery, achieving a 93.4% recovery efficiency at 100% strain after just 5 min of rest, in contrast to 59.7% for the control. This remarkable stability and recovery result from the synergistic interplay between the covalent polymer framework and the interlocked structure, which work in tandem to preserve network integrity and enable rapid host−guest reformation. Notably, despite this significant improvement, CMIP retains a comparable damping capacity (91% versus 87%) and material toughness (14.8 versus 15.1 MJ m−3), owing to the efficient energy dissipation mechanisms enabled by host−guest dissociation and subsequent sliding motion. This strategy imparts CMIP with unique characteristics, offering a prospective pathway for the development of a diverse array of advanced synergistic materials with enhanced, multifaceted properties.

Glycan fragmentation with collision-induced dissociation (CID) mass spectrometry (MS) leads to a range of specific disassembly mechanisms, which are being reviewed in detail.

Structural alterations in oligosaccharides are often associated with disease, positioning clinical glycomics as an emerging tool for diagnostics. This is most commonly achieved using a controlled collision-induced dissociation (CID) of larger oligosaccharides into fragments and measuring their mass in a mass spectrometer. Due to the complexity of oligosaccharides, and particularly their unusual fragmentation mechanisms, the underlying processes are poorly understood. Deciphering glycan fragmentation and making it understandable is highly desirable and would transform the field of glycomics from an expert technique into a widely applicable tool available to non-specialists. Here, we review the current knowledge of glycan fragmentation mechanisms in CID, with particular emphasis on hexose migrations and the anomeric memory. We discuss challenges and perspectives for future investigations, opening the window to widespread use of glycomics in clinical applications based on a fundamental understanding of glycan fragmentation.

Photo-responsive cyclodextrin-based slide-ring gels are presented, which allow for a reversible modulation of the sliding dynamics. Upon light irradiation, the azobenzene-containing network polymers are isomerized, which alters their binding affinity toward the threaded cyclodextrins. As a result, the macrocycle sliding dynamics change, allowing for a reversible switching of the material's mechanical properties between a stiff and a soft state.

Cyclodextrin-based slide-ring gels (SRGs) have emerged as a promising class of materials owing to their unique topology. Upon mechanical loading, the slidable cross-links of the polymer network freely translocate along the polymer backbone enabling pronounced energy dissipation in the material, which is associated with exceptional ductility and toughness. Despite the critical role of sliding dynamics in defining SRG mechanical properties, attempts to control them have primarily been limited to tuning the overall loading of macrocycles. Further, SRGs that can be triggered via an external stimulus have yet to be reported. In this work, we present light-responsive SRGs based on azobenzene-containing polymers. Reversible photoswitching of the azobenzenes modulates the sliding dynamics of the threaded α-cyclodextrin (α-CD) macrocycles. By using UV–Vis and circular dichroism spectroscopy, we show that α-CDs readily bind to the azobenzenes along the polymer backbone in the E configuration. Upon light irradiation, and thus isomerization to the Z isomer, the macrocycles no longer interact with the azobenzenes, allowing them to freely translocate along the polymer backbone. As a result of this E to Z isomerization and difference in sliding dynamics, the mechanical properties of the SRGs reversibly alternate between a stiff and a soft state.

An exposed Au atom on Au(111) in Au52 nanoclusters and as-formed surface/interface environment were constructed by introducing nonaromatic ligand. In situ characterizations and simulations confirmed the activation of CO2 and the accelerated protonation of strongly hydrogen-bonded water by the surface/interface modification, leading to pH-universal electrocatalysis with high activity, selectivity, and durability.

The control of surface and interface structures in nanocatalysts is a promising strategy for enhancing catalytic performance, but significant challenges persist in achieving precisely designed active sites or environments on the surface/interface of fully protected metal nanoclusters. In this study, we report the construction of an exposed Au atom on Au(111) and the formation of a unique surface/interface environment on the Au52 cluster via a cyclopentanethiol-etching strategy. Theoretical calculations and in situ attenuated total reflection infrared adsorption spectroscopy reveal that the exposed Au atom facilitates CO2 activation, while the tailored surface/interface environment promotes the accumulation of strongly hydrogen-bonded water, which can be validated by the molecular dynamic simulation, thus enhancing proton transfer and suppressing hydrogen evolution reaction (HER). Notably, the surface/interface-modified Au52 cluster showcases high activity, selectivity, and durability across pH-universal (acidic, neutral, and alkaline) electrolytes, providing new insights for designing high-performance electrocatalysts at atomic level.

We find that the tip-enhanced Raman signal (TERS) is angularly distributed and vibrational mode specific. The radiation pattern in the back focal plane (BFP) of vertical or parallel Raman dipoles is strongly influenced by the near-field in the TERS nanogap, while the emission is guided into the far-field with high directionality by the tip-sample antenna; however, with significant differences in the emission angle, intensity, and the divergency. .

Despite intensive research in tip-enhanced Raman spectroscopy (TERS), the angular distribution of Raman scattering in the TERS gap remains experimentally unreported leaving its relevance to the TERS signal formation to be seldomly discussed. Here, we investigate the angular distribution of the tip-enhanced Raman signal in the Fourier plane using a model system composed of flat-lying cobalt (II) hexadecafluoro-phthalocyanine (CoPcF16) molecules physically adsorbed on a smooth gold surface. Both in-plane and out-of-plane vibrational modes are observed, where the out-of-plane Raman modes at about 678 and 740 cm−1 have different angular intensity distributions than those of in-plane Raman modes at 1309 and 1373 cm−1. We interpret the angular spectrum of the TERS signal considering the molecular vibrational modes computed with density functional theory (DFT) for the free and gold-deposited molecule, and the directed Raman scattering by the gap-mode predicted by finite-difference time-domain (FDTD) simulations. We contend that the TERS gap directs the Raman vibrational modes differently, leading to distinct angularly distributed Raman scattering intensities. These findings emphasize the nonnegligible role of the TERS detection scheme in understanding spectral features, such as the relative peak intensity ratio variations for studying molecular orientations, or for monitoring chemical reactions.

Incorporation of silicon is systematically explored as a sustainable strategy to design weakly solvating electrolytes for lithium-based batteries. After identifying a promising molecular structure via computational screening, coordination spheres and their correlation with electrochemical key performance indicators are compared between electrolyte formulations, revealing that negative hyperconjugation enhances their oxidative stability.

High concentrations of conducting salt in electrolyte formulations enhance the agglomeration of ionic species, which has been demonstrated to yield anion-derived electrode–electrolyte interphases and improved reversibility in several battery configurations. However, industrial application of these electrolytes may be limited due to high costs of electrolyte conducting salts. Here, weakly solvating electrolyte solvents with tailored coordination strength have been established as an approach to achieve ionic agglomeration at moderate conducting salt concentrations and without per-fluorinated diluents. However, the inevitable presence of uncoordinated solvent molecules in this electrolyte concept renders them susceptible to oxidative decomposition. Although previous efforts demonstrated fluorination as an effective design strategy to tailor the oxidative stability of weakly solvating electrolytes, the per-fluorinated solvents are toxic and harmful to the environment. Herein, the incorporation of silicon is evaluated as an eco-friendly approach to dispel electron density of the oxygen lone pair. Though steric demand of substituents is already sufficient to tailor the coordination strength, negative hyperconjugation effectively expands the oxidative stability limit of weakly solvating electrolytes. Combining ion agglomeration and intrinsic oxidative stability, the herein introduced weakly solvating electrolyte enables a notable improvement of reversibility under eco-friendly conditions, presenting a valid alternative to fluorinated electrolyte solvents.

Triphenylchlorosilane (Ph3SiCl) was developed as a tetrachlorosilane surrogate for the iterative and controllable ligation of four different alcohols to one silicon center to generate fully heteroleptic tetraalkoxysilanes. Mechanistic studies revealed the unusual transformations of Wheland intermediates into both silicon cations and silylated phenylhalonium ions in low and comparable activation barriers.

While critical and indispensable in diversified areas, organosilicon compounds are not naturally occurring and all rely on chemical synthesis. The de novo synthesis of them via quadruple substitutions of tetrachlorosilane was one of the most straightforward and common practices but confronted over-substitution challenges for heteroleptic silanes, especially the ones with four different substituents. Although selective and iterative substitutions at silicon have achieved notable achievements, methods for fully heteroleptic tetraalkoxysilanes are still lacking. Herein, we established the key dephenylative etherification reaction coupling phenylsilanes and alcohols to alkoxysilanes and then developed triphenylchlorosilane (Ph3SiCl) as the surrogate to tetrachlorosilane for the iterative and controllable ligation of four different alcohols to one silicon center as fully heteroleptic tetraalkoxysilanes. Mechanistic studies revealed the unusual transformations of Wheland intermediates into both silicon cations and silylated phenylhalonium ions in low and comparable activation barriers.

Highly efficient ultra-deep-blue TADF emitters were developed through the construction of multipathway charge transfer characteristics. OLEDs employing the optimized molecule as the terminal emitter and as a sensitizer exhibit high-performance deep-blue electroluminescence, achieving EQEs of up to 24.7% and 37.9%, with corresponding CIE-y values of 0.038 and 0.106, respectively.

BT.2020-compliant deep-blue emitters for organic light-emitting diodes (OLEDs) are in high demand to achieve a wide color gamut for ultrahigh-definition displays. Herein, we report deep-blue thermally activated delayed fluorescent emitters featuring a unique donor1-donor2-acceptor (D1-D2-A) molecular configuration in which C1-N linked carbazole derivatives serve as dual-function donors and an oxygen-bridged triarylboron unit acts as the acceptor. The new design strategy focuses on constructing excited states with multipathway charge transfer characteristics—including multiresonance, through-bond, and through-space charge transfer—by precisely tuning the relative electron-donating strengths of the D1 and D2 units. Experimental and theoretical studies reveal that the optimized emitter, BO-BTC, achieves a well-balanced trade-off among emission efficiency, color purity, singlet–triplet energy gap, and horizontal dipole orientation ratio. Consequently, OLEDs using BO-BTC as the terminal emitter or as the sensitizer for ν-DABNA achieve high-efficiency deep-blue electroluminescence, with external quantum efficiencies of up to 24.7% and 37.9%, Commission Internationale de l’Éclairage-y values of 0.038 and 0.106, respectively.

This study develops boron-doped amorphous bismuth metallene arrays for efficient nitrate-to-hydroxylamine electroreduction. The B-induced p-sp orbital hybridization and amorphous structure modulate the electronic configuration and increase active site density, thus optimizing intermediate adsorption and H* generation while lowering the energy barrier of the potential determining step. The catalyst achieves 85.3% NH₂OH Faradaic efficiency (FE) at −0.4 V versus RHE, which further rises to nearly 100% under pulsed potential operation, surpassing most reported systems.

Electrochemical hydroxylamine (NH2OH) synthesis from NOx under ambient conditions presents a sustainable alternative to energy-intensive industrial methods, but its selectivity remains limited by unbalanced active hydrogen (H*) supply and intermediate adsorption. Herein, we develop boron-doped amorphous Bi metallene arrays for efficient nitrate-to-NH2OH electroreduction. In situ spectroscopy and theoretical calculations reveal that the amorphous structure and B-induced p-sp orbital hybridization modulate the electronic structure, optimizing intermediate adsorption while enhancing H* generation. These synergistic effects collectively reduce the energy barrier of the potential-determining step, significantly improving catalytic activity and selectivity. The catalyst achieves an NH₂OH Faradaic efficiency (FE) of 85.3% at −0.4 V versus reversible hydrogen electrode (RHE). By employing a pulsed potential strategy, the FE further increases to nearly 100%, surpassing most reported counterparts. This work not only proposes a novel catalyst design leveraging amorphous engineering and orbital hybridization but also demonstrates the efficacy of pulsed electrolysis in steering reaction pathways for electrosynthesis.

Crystal engineering and facet engineering were concurrently employed to develop a series of precious-metal-free heterobimetallic MOFs (M-BCA-M', M = Cu+, M' = Zr4+ or Hf4+) for record-high photocatalytic hydrogen production in pristine MOFs. The high performance and crystal-facet dependent behaviors were investigated to provide molecular-level insights into the coordination regulation and morphology control of pristine MOFs for efficient photocatalysis.

Solar-driven water splitting for hydrogen production over metal–organic frameworks (MOFs) is particularly attractive yet remains a challenge. Here, we report a series of ultra-stable heterobimetallic MOFs (M-BCA-M', M = Cu+, M′ = Zr4+ or Hf4+) for photocatalytic hydrogen production, in which, the Cu(I) species act as the active center, whereas Zr(IV)/Hf(IV) plays an essential role in stabilizing the framework. Uniform MOF crystals with distinct morphologies were obtained, showing a rare crystal facet-dependent photocatalytic behavior. The octahedral MOF crystals denoted as Cu-BCA-Hf-O with the exposure of only {101} and {011} facets exhibit a record-high hydrogen production rate (49825.71 µmol g−1 h−1) among pristine MOF photocatalysts. The exceptional performance of Cu-BCA-Hf-O can be primarily attributed to its superior photogenerated carrier transfer ability and abundant active sites exposed on the crystal surface. This study provides molecular-level insights into the coordination regulation and morphology control of MOFs for highly efficient photocatalysis, highlighting the promising future of pristine MOF photocatalysts.

The hierarchical pore channels of MIL-100 confine LiI to form a conductive ionic network, while its triple-level cross-linked multi-stage porous restricts TFSI⁻ anion mobility, enabling rapid Li⁺ transport and uniform deposition by optimizing ion flux and suppressing space charge effects.

Solid-state lithium metal batteries (SSLMBs) are hindered by limited ionic conductivity, heterogeneous lithium flux and interfacial instability of solid-state electrolytes. Herein, we report a hierarchical ion-transport network formed by confining lithium halides (LiX, X═Cl, Br, I) within the mesoporous cages of MIL-100(Al), synergistically integrated with a PVDF-HFP polymer matrix. The 3D interconnected pores (0.5–1 nm) of MIL-100(Al) not only spatially confine anions via size-selective sieving but also enable continuous Li⁺ transport through tunable host–guest interactions between the Lewis-acidic metal nodes and lithium halides. Among these, the LiI-embedded composite (E-LiI) exhibits a high Li⁺ transference number (0.88 at 25 °C) and favorable interfacial kinetics, attributed to strong anion coordination and homogeneous Li⁺ plating. Structural characterizations confirm uniform LiX distribution within the MOF framework. In addition, density functional theory (DFT) calculations and COMSOL simulation elucidate halogen-dependent desolvation energetics and Li+ transport kinetics. SSLMBs employing E-LiI electrolytes demonstrate exceptional cycling stability (capacity retention ∼100% after 600 cycles at 2C) with high-voltage cathodes and wide-temperature adaptability. This work advances the rational design of multi-scale ion-conductive frameworks and the pivotal role of lithium halide in regulating Li deposition kinetics, offering a transformative strategy for high-energy-density solid-state battery systems.

Regiodivergent photocatalytic annulation of gem-difluorocyclopropyl urea with olefins or bicyclobutanes (BCBs) has been developed. The regioselectivity is controlled by the proper choice of counteranion of the cationic iridium photocatalyst and solvent. This protocol enables straightforward access to diverse cyclic amino hydrocarbons, including functionalized bicyclic scaffolds of distinct three-dimensional architectures, with precise deployment of the gem-difluoromethylene groups, cultivating a chemical space for bioisosteres.

Regiodivergent synthesis is a powerful strategy for expanding chemical space. Given the significance of fluorine-containing molecules in pharmaceutical sciences, a regiodivergent [3+2] cycloaddition of gem-difluorocyclopropyl urea to olefins and [1.1.0]-bicyclobutanes was developed by employing cationic iridium complexes as photocatalysts under visible-light irradiation. By properly selecting a counteranion of the photocatalyst and tuning the reaction conditions, each regioisomeric cyclic hydrocarbon with a defined gem-difluoromethylene disposition was directly assembled with high selectivity. Mechanistic elucidation revealed the critical relevance of the basicity of the photocatalyst counteranion to the regiochemical outcome. The reaction diverges depending on the intervention of deprotonation of the initially generated urea radical cation by the pairing anion to form the corresponding neutral radical; this not only governs the regioselective ring opening of the cyclopropane moiety but also modulates the relative reactivity of the two resulting terminal carbon radicals, thereby dictating the dominant pathway.

This study reveals that MarE, a heme-dependent aromatic oxygenase, favors dioxygenation of β-methyl-l-tryptophan in the absence of ascorbate and demonstrates how structural and redox tuning shifts its reactivity toward selective monooxygenation, yielding a 2-oxindole scaffold. These findings offer new insights into enzyme-controlled indole oxidation in tryptophan-derived natural products.

MarE, a heme-dependent aromatic oxygenase with a histidyl axial ligation, catalyzes the monooxygenation of β-methyl-l-tryptophan to form a 2-oxindole scaffold central to maremycin biosynthesis. Although structurally similar to tryptophan 2,3-dioxygenase (TDO), which initiates l-tryptophan catabolism via dioxygenation, MarE exhibits distinct reactivity modulated by ascorbate. While ascorbate has no effect on TDO, it promotes selective monooxygenation by MarE. In its absence, MarE favors dioxygenation and formation of pyrroloindoline products, revealing latent catalytic versatility. Active-site loop sequences differ between the two enzymes, SLGGR in MarE versus GTGGS in TDO, prompting loop-swapping experiments to probe structure-function relationships. Substituting GTGGS in TDO to MarE-like sequences (GTGGA or SLGGS) shifted reactivity toward monooxygenation and formation of C3-hydroxylated, non-oxindole products that underwent further cyclization into tricyclic structures. Conversely, replacing SLGGR in MarE with GTGGS resulted in enhanced C2,C3-dioxygenation nearly 4-fold. These results underscore the active-site loop as a key determinant of oxidation outcome, alongside the modulatory role of ascorbate. By revealing the true catalytic identity of MarE and delineating the roles of small-molecule effectors and loop architecture, this study advances mechanistic understanding and predictive capabilities within the oxygenase superfamily.

Fully exposed silver clusters were successfully anchored on poly(heptazinimide), demonstrating exceptional photocatalytic activity toward H2O2 generation in pure water from O2. Systematic evaluation revealed that it also exhibited significantly enhanced performance compared to their single-atom counterpart due to superior electronic properties and synergetic effect between adjacent Ag atoms.

Photocatalytic production of H2O2 in pure water holds great potential for sustainable industry. However, this prospect is greatly hindered by its sluggish reaction kinetics involving multistep electron transfer and unstable intermediates. Herein, the fully exposed silver (Ag) clusters were anchored on poly(heptazinimide) (PHI) catalyst, forming a new kind of fully exposed cluster catalysts (FECCs), which can boost photocatalytic generation of H2O2 in pure water, with a rate up to 1075.5 µmol g−1 h−1, surpassing its Ag single atoms counterpart and many recent-reported state-of-the-art photocatalysts. In situ characterization and DFT analysis showed that fully exposed Ag clusters can form the electron-rich centers and optimize the binding energy of the O2 and proton H, which in turn enhances the protonation process of *OOH, reducing the energy barrier of key steps, and finally leading to a high yield of H2O2. Interestingly, its Ag single-atom counterpart was favorable for decomposing the H2O2 into ·OH. Thus, Ag FECCs achieve significantly enhanced tetracycline degradation efficiency with the strategic incorporation of Ag single atoms.

This review comprehensively summarizes the synthesis strategies, structural characteristics, and structural regulation strategies of metal-covalent organic frameworks (MCOFs), as well as their electrochemical energy storage performance in various energy storage devices (LIBs, LMBs, ZABs, Li–CO2 batteries, LSBs, ZIBs, and SCs).

Metal-covalent organic frameworks (MCOFs), which can integrate the properties of metal-organic frameworks (MOFs) and covalent organic frameworks (COFs), exhibit high stability, adjustable pore structures, and catalytic activity of metal sites owing to the synergistic interaction between metal sites and covalent backbones. In this regard, MCOFs have gained significant attention as promising electrode materials, where metal ions (Mn+) function as molecular structure switches, providing MCOFs with diverse active sites and modifying their charge density by incorporating different Mn+, thereby imparting unique energy-storage properties to MCOFs. Furthermore, by optimizing the synthesis strategies of MCOFs, their topological and dimensional structures can be regulated to ensure the stability of the MCOFs. In the challenging landscape of energy storage, MCOFs have surpassed the performance limitations of traditional COFs. Through precise atomic-level control of metal sites and innovative design of dynamic covalent chemistry, they can significantly enhance the performance of batteries, achieving remarkable performance in lithium-ion batteries (LIBs), lithium–sulfur batteries, and other applications. This review systematically summarizes the research advancements of MCOFs in high-performance energy storage devices, including lithium-ion, Li–CO2, and Zn-ion batteries. In addition, it examines the synthesis strategies, structural regulation, and structural characteristics of MCOFs to address the challenges encountered in various energy storage devices.

The photoluminescence quantum yield (PLQY) of one-dimensional (CH3)4NMnCl3 (TMMC) doped with Cd2+ remains consistently high (∼95%) across the studied composition range (x = Cdx/Mn1-x = 0–0.22). By combining PL lifetime measurements, high-pressure optical absorption spectroscopy, and X-ray diffraction structural analysis, we demonstrate that the PLQY exhibits only minimal dependence on x. This finding contrasts with recent reports,1 claiming that the PLQY initially rises with Cd2+ content up to x = 0.08, then declines sharply from 95% to 77% at x = 0.22.

The photoluminescence quantum yield (PLQY) of tetramethyl ammonium manganese(II) chloride, (CH3)4NMnCl3 (TMMC), doped with Cd2+/Cu2+ is analyzed through photoluminescence measurements, X-ray diffraction, optical absorption, and time-resolved excitation and emission under hydrostatic pressure. Contrary to recent studies reporting a PLQY increase up to x = Cdx/Mn1-x = 0.08 followed by a decline (from 95% to 77% at x = 0.22),1 we demonstrate that the PLQY remains consistently high (≥95%) across the concentration range x = 0–0.22.

A butterfly-shaped UV-transparent hybrid birefringence crystal, (C10H6NO2)2SbF (QCSF), with a record-breaking birefringence of 0.87 at 546 nm, surpassing all previously reported halide birefringent crystals with SCALPs, was successfully designed and synthesized through a dual-sided multidentate coordination strategy.

Achieving ultrahigh birefringence in UV-transparent materials remains fundamentally constrained by the trade-off between strong optical anisotropy and wide bandgap transparency. Herein, we report a dual-sided multidentate coordination (DMC) strategy to construct two butterfly-shaped UV organic–inorganic hybrid crystals—(C6H4NO2)2SbF (PCSF) and (C10H6NO2)2SbF (QCSF)—in which planar π-conjugated bidentate ligands symmetrically chelate stereochemically active lone pair (SCALP) Sb3+ centers. This coordination architecture enforces coplanar alignment of optical functional units and promotes dense π–π stacking, thereby significantly enhancing macroscopic birefringence. Notably, QCSF achieves a record-high birefringence of Δn = 0.87 at 546 nm, surpassing all previously reported lone-pair-containing halide crystals with UV transparency. The exceptional optical performance is attributed to the unique [SbN2O2F] coordination geometry, near-planar molecular configuration, and extended π-electron delocalization. First-principles calculations reveal that the observed anisotropy stems from synergistic orbital coupling between the Sb centers and the π-conjugated organic ligands. This work introduces a broadly applicable molecular design paradigm for next-generation birefringent crystals that simultaneously offer high optical anisotropy and UV transparency.