Acetylene (C2H2) and ethylene (C2H4) are essential raw materials in the chemical industry, and producing them in high purity necessitates the efficient separation of C2H2/CO2 and C2H2/C2H4 mixture─a challenging task due to their similar physical properties. Herein, we report the first example of a ligand-functionalized borane-cluster-based hybrid supramolecular metal-organic framework, denoted BSF-12, which integrates a hydroxyl-functionalized organic ligand (dpg) with inorganic boron cluster anions. This dual-functionalization strategy endows BSF-12 with exceptional adsorption and separation performance. The material exhibits high IAST selectivities of 12.0 for C2H2/CO2 (50/50, v/v) and 11.7 for C2H2/C2H4 (1/99, v/v), outperforming many previously reported high-performance adsorbents. BSF-12 demonstrates outstanding stability, maintaining its structural integrity after exposure to air and water for 10 days. Dynamic breakthrough experiments confirmed its practical separation capability and excellent cyclic stability. DFT calculations reveal that the synergistic cooperation between the functional hydroxyl groups from the dpg ligand and the hydride sites from the [B12H12]2- anion creates a robust recognition environment for C2H2, driving its selective adsorption. This work establishes a new paradigm for the design of advanced boron cluster-based frameworks for key gas separations.

Mechanically robust hydrogels hold great promise in structural engineering and materials fields. However, high strength and high toughness are usually mutually exclusive, and simultaneously achieving both properties in a hydrogel remains challenging. Inspired by the structural design of double-network hydrogels and nano-reinforcement strategies, herein, we develop an ultratough hydrogel featuring an organic-inorganic bicontinuous network structure. Specifically, liquid-like calcium phosphate clusters (CPC) and polyvinyl alcohol (PVA) molecular chains are crosslinked at the ionic-molecular level to form an organic-inorganic bicontinuous network, which imparts the resulting PVA/CPC hydrogel with outstanding mechanical properties (tensile strength: 32.89 ± 4.67MPa, toughness: 108.50 ± 19.27MJ m- 3), surpassing those of most existing high-performance hydrogels. Furthermore, the PVA/CPC hydrogel demonstrates exceptional energy absorption and dissipation capabilities, enduring 100 000 cycles of stretching in water without fracture, thus exhibiting remarkable fatigue resistance. Damaged PVA/CPC hydrogel can be repaired via organic-inorganic re-crosslinking. These superior mechanical properties provide a solid foundation for the large-scale application of the PVA/CPC hydrogel in soft robotics, energy-absorbing cushioning materials. The proposed organic-inorganic crosslinking strategy, based on liquid-like inorganic ionic clusters and polymer chains, offers a promising approach for producing high-performance bicontinuous network structural materials.

Carboranes are inorganic clusters exhibiting 3D aromaticity, which imparts exceptional thermal stability, low electrophilicity, and a large HOMO-LUMO gap. The isomerization of carboranes at ambient temperature remains, in many cases, a synthetic challenge. In this work, we present a new method based on the reactivity of closo-1,2-C2B8H10 with various types of carbenes. Such reactions yield arachno-shaped carboranes, which undergo facile dihydrogen elimination at low temperatures, accompanied by C-C bond cleavage and migration of the carbon atoms. These compounds react in the reverse manner compared to common neutral boranes, and their basicity is governed by the electronic parameters of the coordinated carbene molecules. Treatment with hydrogen chloride can thus leave the neutral carborane intact or protonate it once or even twice. The doubly protonated carboranes immediately undergo chlorination by the chloride anion. Thus, the carbene-carborane adducts undergo hydrogen-induced redox changes.

Circularly polarized luminescence (CPL) provides an additional degree of freedom for light manipulation beyond intensity and wavelength and is essential for advanced photonic technologies. Chiral hybrid metal halides (HMHs) have recently emerged as promising CPL-active materials. However, the simultaneous realization of high efficiency near-infrared (NIR) emission and strong CPL remains challenging. Here, we report an enantiomeric pair of zero-dimensional hybrid copper bromides, (18C6@S/R-CHEA)2Cu4Br6 (abbreviated as S/R-CHEACuBr, 18C6 = 18-crown-6, S/R-CHEA = (S/R)-1-cyclohexylethanamine), in which protonated S/R-CHEA+ is coordinated with 18C6 to form the bulky umbrella-type supramolecular cations. Such unique cations effectively isolate the inorganic [Cu4Br6]2- emissive clusters and induce pronounced distortions of inorganic clusters. As a result, the obtained materials show strong circularly polarized near-infrared (CP-NIR) emission with photoluminescence quantum yields exceeding 50% and a high dissymmetry factor up to 6.8 × 10-2. Furthermore, light-emitting diodes based on these materials exhibit high output power and distinct CP-NIR signals, offering new opportunities for NIR imaging and secure information technologies.

ABSTRACT Circularly polarized luminescence (CPL) provides an additional degree of freedom for light manipulation beyond intensity and wavelength and is essential for advanced photonic technologies. Chiral hybrid metal halides (HMHs) have recently emerged as promising CPL‐active materials. However, the simultaneous realization of high efficiency near‐infrared (NIR) emission and strong CPL remains challenging. Here, we report an enantiomeric pair of zero‐dimensional hybrid copper bromides, (18C6@ S/R ‐CHEA) 2 Cu 4 Br 6 (abbreviated as S/R ‐CHEACuBr, 18C6 = 18‐crown‐6, S/R ‐CHEA = ( S/R )‐1‐cyclohexylethanamine), in which protonated S/R ‐CHEA + is coordinated with 18C6 to form the bulky umbrella‐type supramolecular cations. Such unique cations effectively isolate the inorganic [Cu 4 Br 6 ] 2− emissive clusters and induce pronounced distortions of inorganic clusters. As a result, the obtained materials show strong circularly polarized near‐infrared (CP‐NIR) emission with photoluminescence quantum yields exceeding 50% and a high dissymmetry factor up to 6.8 × 10 −2 . Furthermore, light‐emitting diodes based on these materials exhibit high output power and distinct CP‐NIR signals, offering new opportunities for NIR imaging and secure information technologies.

Metal-Organic Frameworks (MOFs) have attracted widespread attention for their applications in water-related contexts. A comprehensive understanding of the molecular-level interactions between water and MOFs is crucial for guiding molecular design and optimizing water-related applications. Water can act as a passive guest, interacting weakly with open metal sites or polar linkers without altering the framework, or as a reactive species that cleaves the dative bonds between inorganic clusters and organic linkers, leading to irreversible degradation. In this work, we uncover a significant impact of water on the metal-linker linkage in UiO-66, a prototype MOFs which is considered highly stable with water. The adsorption of water molecules in UiO-66 results in the displacement of firmly attached carboxylate groups of the linker, thereby transforming them into dangling carboxylate groups. These dangling groups are stabilized by water molecules and μ3-OH through hydrogen bonding. Remarkably, this structural transformation is reversible upon water removal. These findings were elucidated through the integration of multidimensional solid-state NMR, cutting-edge dynamic nuclear polarization (DNP) techniques, and computational calculations. By challenging conventional wisdom, our research has introduced a reversible molecular structure evolution scenario, redefining the understanding of water-MOF interactions.

The escalation of thermal runaway in lithium-ion batteries presents severe safety hazards that necessitate advanced monitoring protocols to ensure early warning of potential failures. Carbon dioxide (CO2) is released during preliminary decomposition well before catastrophic failure occurs, thereby providing a strategic advantage for early-stage warning. Consequently, identifying materials with high-selective CO2 recognition is an essential prerequisite for developing reliable sensing platforms. This study integrates Grand Canonical Monte Carlo simulations with Random Forest (RF) models to systematically screen 1470 MOFs from the CoRE-MOF 2019 database. The screening process evaluates selective CO2 recognition under multicomponent competitive adsorption conditions involving CO2, C2H4, and O2. The performance evaluation is based on working capacity, selectivity, and the trade-off between working capacity and selectivity (TSN). The RF model achieves high predictive accuracy, with tested R2 exceeding 0.92 on the test samples. Shapley Additive Explanations (SHAP) interpretability analysis identifies Q0st(CO2), Q0st(C2H4), WEPA, KH(C2H4), and ETR as key performance drivers. The results indicate that CO2 selectivity is constrained by the binding strength of competing C2H4. Optimal materials tend to have hard Lewis acid centers and polar inorganic clusters to minimize non-specific π-interactions with interfering species. Top-performing MOFs require balanced structural features, concentrating in moderate surface areas (965-1975 m2/g), narrow pore windows (PLD ≈ 4-7 Å, LCD ≈ 5.5-9.6 Å), high void fractions above 0.6, and low densities below 1.3 g/cm3. AJOTEY emerges as the optimal candidate with a TSN of 6.43 mol/kg, combining substantial working capacity (4.57 mol/kg) with strong selectivity (25.52). These results will accelerate the discovery of sensing materials and provide a practical pathway for MOF-based CO2 sensor development to enhance lithium-ion battery safety.

Inorganic molecular clusters (IMCs) belong to a trending class of materials with unique structures and properties. Due to having a gap among the cages, they attract the attention of many researchers. This study is carried out in order to investigate the mechanism of adsorption of CO2, SO2, NH3 and CH4 gases on Sb3(TM)O6 (where TM is Sc, Ti, V, Cr, Mn, Fe, Ni, and Co) molecular clusters for gas-sensing applications. The structural and electronic properties, along with chemical stability, are determined through density functional theory (DFT) and molecular dynamics (MD) simulations. The adsorption energy of Sb3(TM)O6 for the CO2, SO2, NH3 and CH4 gases is calculated. The properties and charge analysis of fully loaded clusters are studied through quantum topology of atoms in molecule (QTAIM) and charge-transfer integrals.

Metabolomic analysis of biological samples is an important direction in the development of diagnostic methods for chronic kidney disease (CKD) in children. Hydrophilic interaction chromatography tandem mass spectrometry (HILIC–MS/MS) is widely used in metabolomics; however, this method is associated with the problem of matrix effect (ME). In this study, we evaluate the ME arising from the analysis of nine low-molecular weight polar marker metabolites of CKD under HILIC conditions in samples of new model and real urine. Amino acids and their polar metabolites involved in the pathophysiologic processes of CKD development were selected as nine biomarkers to be determined. The ME on the first quadrupole was assessed by calculating the ratio of the coelution parameters of low-molecular weight clusters consisting of buffer formate anions and salt cations in urine and L-valine- 13 C 5 standard. In real urine, the signal intensity of the L-valine- 13 C 5 standard was reduced by more than 50% relative to methanol when the cluster signal was superimposed, whereas in artificial urine, the suppression effect was comparable to the real sample under all elution conditions. The addition method was also applied to evaluate the ME of isotope-labeled endogenous markers in real and artificial matrices. It was shown that a preliminary assessment of signal quenching can be studied on model urine of a new composition. The results demonstrate the importance of evaluating the optimal signal resolution of not only marker compounds but also inorganic clusters, which can significantly reduce the analysis errors under real matrix conditions. The evaluation of this effect should improve the accuracy of polar metabolite analysis in real samples in CKD metabolomics. The applied artificial urine samples showed comparable ME to the real sample, which confirms its promising potential for optimizing the HILIC–MS/MS analysis conditions.

Flexible composite polymer electrolytes (CPEs) are promising candidates for high‐energy all‐solid‐state lithium metal batteries, owing to their superior processability, excellent electrochemical performance, and enhanced safety. Nevertheless, conventional CPEs face challenges such as lithium‐ion blocking and aggregation from inert fillers, hindering ion transport. To address these issues, highly dispersed materials need optimization in polymer matrices. In this study, a new strategy is introduced to introduce sub‐1 nm inorganic cluster chains into poly(ethylene oxide) based electrolytes. These ultra‐thin highly dispersed cluster chains eliminated the Li blocking region and aggregation‐induced barrier, formed a 3D network, and realized the efficient conductivity of Li+. By engineering La vacancies into the cluster chains of Ta‐doped LaOOH crystals, low‐energy migration pathways are created. This optimized electrolyte achieves the ionic conductivity of 0.65 mS cm−1 at 60 °C and the lithium transference number of 0.47. Electrochemical testing shows outstanding stability: Li||LTPE||Li symmetric cells maintain stable Li plating and stripping for 2000 h, and LiFePO4||LTPE||Li cells achieve 138.5 mAh g−1 with 93.4% capacity retention after 2000 cycles at 2C. Furthermore, the pioneering application of in situ conductive atomic force microscopy enables unprecedented characterization of temperature‐dependent morphological evolution and heterogeneous ion transport dynamics in solid electrolytes.

Polyoxometalates (POMs) represent a broad class of anionic inorganic (V, Mo, W) clusters with versatile structures of chemical and physical properties. POMs are inhibitors of many enzymes, including P-type ATPases, well-known to be a target of several approved drugs. Herein, two new hybrid POMs with Mo and mixed V/W, namely (C2H8N1)6[V2Mo18O62].3H2O (1) and (C4H16N3)4[V2W4O19]3.12H2O (2), were synthesized via wet chemical methods in aqueous solution, and their purity was confirmed and characterized by single X-ray diffraction and infrared spectroscopy. The cations are dimethylammonium ((C2H8N)+) and diethylenetriammonium ((C4H16N3)3+), respectively. POMs biological activities were investigated, specifically their inhibitory potential against Ca2+-ATPase. The sarcoplasmic reticulum Ca2+-ATPase activities were measured spectrophotometrically using the coupled enzyme pyruvate kinase/lactate dehydrogenase assay. For the Ca2+-ATPase activity, Dawson (1) showed an IC50 value of 3.4 μM, whereas Lindqvist (2) displayed a value of 45.1 μM. The Ca2+-ATPase inhibitory potential of these POMs can be correlated with the net charge (namely 6- and 4-) and the charge density (namely 0.33 and 0.67). A structure–activity-relationship was established for a series of 17 POMs Ca2+-ATPase inhibitors correlating IC50 values and POMs net charge and POMs charge density. The described features make Dawson (1) and Lindqvist (2) attractive POMs in a wide range of chemistry fields as well as in biomedical applications.

Abstract Proton conductors with engineered charge‐assisted hydrogen‐bonding networks are pivotal for advancing proton exchange membrane fuel cells (PEMFCs). Herein, a novel proton‐conducting supramolecular clusters, ([Bi 6 O 5 (OH) 3 ] 2.24 [PW 12 O 40 ] 1 [NO 3 ] 2.4 [H 3 O] 5.8 , BPN) has been synthesized and characterized. Molecular dynamics (MD) simulations reveal that charge‐assisted dynamic O─H⋯O hydrogen bonds mediate the supramolecular assembly, while water molecules facilitate proton transport pathways. The material exhibits a maximum proton conductivity of 0.12 S cm −1 at 90 °C and 97% (RH) relative humidity, which is comparable to that of Nafion. The spin‐lattice relaxation time ( T 1 ) of the Bi–O adsorbed protons is significantly shorter than that of the W‐O adsorbed protons, indicating that the protons at the Bi–O sites have a higher migration rate. 1 H magic‐angle spinning NMR ( 1 H MAS NMR) and density functional theory (DFT) calculations reveal [Bi 6 O 8 ] enhances proton mobility, while [PW 12 O 40 ] stabilizes transition states, lowering the activation barrier to 0.14 eV. The BPN‐Nafion hybrid membrane enhances direct methanol fuel cell performance with an open‐circuit voltage of 0.82 V and power density of 86 mW cm −2 . This integrative design strategy—synergizing inorganic cluster units with dynamic hydrogen‐bonding networks—establishes a scalable platform for developing PEMFC materials with programmable proton transport pathways and improved operational stability.

Proton conductors with engineered charge-assisted hydrogen-bonding networks are pivotal for advancing proton exchange membrane fuel cells (PEMFCs). Herein, a novel proton-conducting supramolecular clusters, ([Bi6O5 (OH)3]2.24[PW12O40]1[NO3]2.4[H3O]5.8, BPN) has been synthesized and characterized. Molecular dynamics (MD) simulations reveal that charge-assisted dynamic O─H⋯O hydrogen bonds mediate the supramolecular assembly, while water molecules facilitate proton transport pathways. The material exhibits a maximum proton conductivity of 0.12S cm-1 at 90°C and 97% (RH) relative humidity, which is comparable to that of Nafion. The spin-lattice relaxation time (T1) of the Bi-O adsorbed protons is significantly shorter than that of the W-O adsorbed protons, indicating that the protons at the Bi-O sites have a higher migration rate. 1H magic-angle spinning NMR (1H MAS NMR) and density functional theory (DFT) calculations reveal [Bi6O8] enhances proton mobility, while [PW12O40] stabilizes transition states, lowering the activation barrier to 0.14eV. The BPN-Nafion hybrid membrane enhances direct methanol fuel cell performance with an open-circuit voltage of 0.82V and power density of 86mW cm-2. This integrative design strategy-synergizing inorganic cluster units with dynamic hydrogen-bonding networks-establishes a scalable platform for developing PEMFC materials with programmable proton transport pathways and improved operational stability.

ABSTRACT Polyoxometalates (POMs) are considered highly suitable for electrochemical energy storage due to their advantageous structural and electrochemical features. As inorganic molecular clusters, POMs exhibit high thermal and chemical stability, tunable redox potentials, and a wide range of compositions, making them attractive for use in electrochemical storage devices. This work systematically explores the unique advantages of POMs‐based materials, including their redox reactions and charge storage mechanisms. The introduction of conductive polymers into electrochemical devices shows remarkably enhanced performance, and the assembled solid‐state capacitor 1‐CC@PANI‐SC achieved a maximum specific capacitance of 86.8 mAh g −1 , an energy density of 14.16 Wh kg −1 with power density of 802.57 W kg −1 . This study provides a promising insight for the design and synthesis of purely inorganic POMs and applications in energy storage devices.

Low-dimensional (LD) organic metal halides (OMHs) composed of organic cations and metal halide networks have been extensively investigated due to their excellent photophysical properties. The effect of organic cations on the electronic structure of the LD-OMHs was investigated by reacting CuBr with 1,4-diazabicyclo[2.2.2]octane salts having different alkyl chain lengths, leading to the formation of two new 0D-OMHs with similar structures containing a rare [Cu4Br8]4- clusters. The only structural difference observed in the metal halide networks was the spacing of the metallic clusters due to the length of the alkyl chains. Such a difference significantly impacts the emission and photoluminescence quantum yields (ΦF = 98% vs 51%), exhibiting long emission decay times of 79.7 μs (1) and 72.6 μs (2), respectively. Photophysical properties and crystal structure analysis clearly reveal that the alkyl chain length of organic cations affects the electric field around the inorganic cluster, leading to the distortion of the inorganic clusters and resulting in the emission intensities, wavelengths, and band broadnesses.

Multicolor luminescent materials have gained widespread attention due to their promising applications in anticounterfeiting and information security. Herein, two novel zero-dimensional copper-based halides, (C5H11N3)2Cu3Cl7·H2O and (C5H11N3)2Cu2Br6, with tunable yellow and blue dual-color emission via a halogen regulation strategy have been synthesized. Both crystals exhibit a zero-dimensional structure that is composed of isolated organic [C5H11N3]2+ cations and an inorganic [Cu3Cl7]4-/[Cu2Br6]4- cluster. Notably, broad emission peaks located at 549 and 457 nm, large Stokes shifts of 216 and 156 nm, and long lifetimes of 10.15 and 13.45 μs that separately correspond to yellow and blue emission were determined for (C5H11N3)2Cu3Cl7·H2O and (C5H11N3)2Cu2Br6, respectively, which can be ascribed to self-trapped exciton (STE) emission. Furthermore, a higher PLQY of 23.79% was obtained for (C5H11N3)2Cu2Br6 compared to the value of 15.90% for (C5H11N3)2Cu3Cl7·H2O, which may be related to their different inorganic cluster configurations and distortion. To further elucidate the structure-property relationship, density functional theory (DFT) calculations were also conducted, indicating that copper halide clusters predominantly contribute to their optical performances. Taking advantage of the tunable dual-color emission, multiple anticounterfeiting modes were successfully designed to achieve information security. This research offers new insights into modulating the multicolor luminescence of copper-based halides, expanding their potential application in anticounterfeiting.

Rapid Li+ transport channels in composite solid electrolytes (CSEs) are often attributed to organic-inorganic interfaces. However, slow Li+ transport through polymer chains is still dominant due to inefficient interface construction and weak interface interactions. In this study, interface-dominated Li+ transport was achieved in ultracompatible CSEs by modifying sub-1 nm inorganic cluster chains (ICCs) with polyether amine (PEA). The abundant amino groups in PEA made ICCs monodisperse in the PVDF-HFP matrix and form hydrogen bonds with polymer chains. The distribution of organic-inorganic interfaces and interfacial hydrogen bonds was amplified by the multidimensional optimized interfaces. Moreover, the direction of -CF2- groups was regulated by the hydrogen bonds to provide rich and continuous interface interaction sites and local charge accumulation regions for more free Li+ and more Li+ transport pathways, thereby making the Li+ interface transport dominant (52%) for the overall Li+ transport in CSEs. Consequently, the as-obtained composite solid electrolyte exhibits exceptional room temperature ionic conductivity (0.53 mS cm-1), a substantial Li+ transference number (0.65), and a stable cycling performance (95% capacity retention of NCM/Li batteries after 500 cycles at 0.5 C). This work introduces key concepts for the practical application of ICCs and outlines core design principles for composite solid electrolytes.

Abstract The structure-dependent unique host-guest chemistry of the bowl-shaped inorganic vanadium-oxygen cluster anion, [V12O32]4– (V12), is reviewed. The half-spherically ordered square-pyramidal VO5 units form the relatively positively charged concave inside. It stabilizes anionic moiety at the concave, even though the host itself possesses negative charge. Unusual anions such as nitroxyl anion, NO–, and deprotonated nitromethane anion, CH2NO2 –, are also stabilized in V12. The guest-exchange, -removal and -inclusion of the V12 host are demonstrated. The removal of a guest causes a flip of one of the VO5 pyramidal units, and the inclusion retrieves the structure. The incorporation of a bromine molecule induces the polarization of bromine molecule, and it provides brominated products of alkanes with unique selectivity. The lid effect of a cation above the concave controls the depth and orientation of a guest. An inert tetraethylammonium cation acts as a lid. Azide, N3 –, is forced to be laid down in the concave with elliptically distorting the V12 host. The lid cation also affects the oxidation catalytic property of V12.

Functionalized quinones are crucial structural building blocks for synthesizing significant biologically active compounds. The selective catalytic oxidation of low-valent oxygen precursors (including aromatic compounds, phenolic derivatives, and hydroquinone analogs) has been widely recognized as one of the most economically and environmentally favorable approaches for producing functionalized quinones. Polyoxometalates (POMs), as versatile inorganic clusters, have attracted much attention in multidisciplinary fields, especially in catalysis, due to their adjustable structural configuration and acid-base properties, excellent redox properties, as well as remarkable thermal stability, chemical stability, and hydrolysis stability. As a pivotal branch, POM-based heterogeneous catalytic systems not only preserve the inherent, highly active sites of POMs but also establish synergistic catalytic networks through the integration of hybrid components. This paves a new way for achieving material recyclability and green catalytic technology. This review presents a critical analysis of research advances in POM-based heterogeneous catalysts for quinone synthesis over recent decades and systematically proposes optimization strategies from the perspective of material design principles and catalytic processes, aiming to offer molecular engineering theoretical support for the construction of a new generation of catalytic platform.

Polyoxometalates (POMs), which were inorganic metal-oxygen clusters, have demonstrated considerable advancement in the field of bacterial inhibition due to their structural diversity. This study focused on the synthesis of a novel bacteriostatic agent by combining POMs (β2-SiW11V) with fluconazole (FLC) using a hydrothermal method. The sample’s structure was characterized using a range of analytical techniques, including infrared spectroscopy (FT-IR), thermogravimetric analysis (TG), X-ray diffraction (XRD), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS) The bacteriostatic properties of the samples were evaluated using the minimum inhibitory concentration (MIC), and colony counting method. The resulted indicate that β2-SiW11V-FLC exhibited a stronger inhibitory effect on Escherichia coli (E. coli: MIC = 8 μg mL−1) compared to Bacillus subtilis (B. subtilis: MIC = 16 μg mL−1) and Staphylococcus aureus (S. aureus: MIC = 32 μg mL−1). The potential mechanisms of bacterial inhibition were investigated through the observation of bacterial growth. The findings explored that the bacteriostatic agent accelerated the disruption of the cell wall, which facilitating the efflux of solutes from the bacterial cells, ultimately led to bacterial death. The experimental results demonstrated that the inhibitory effect of β2-SiW11V-FKZ on Gram-negative bacteria was superior to that of Gram-positive bacteria.