The methanol-to-olefin (MTO) process offers a sustainable olefin production pathway, but it generates mixed streams containing C3H6/C2H4 in a 2:5 ratio. In this work, we report a series of isostructural microporous MOFs with a 4,8-connected topology, denoted as M-DCPB (M = Mn, V, Ti). The MOFs were constructed from M-2 and M-3 clusters bridged by the isosceles triangular ligand [1,1 ':3 ',1 ''-terphenyl]-4,4 '',5 '-tricarboxylate (H3DCPB). Among the materials, MnV-DCPB showed a C3H6 adsorption capacity of 2.35 mmol g(-1) at 10 kPa, an isosteric heat of adsorption of 29.3 kJ mol(-1), and an IAST selectivity of similar to 11 for C3H6/C2H4 (2:5) at 298 K. Dynamic breakthrough experiments confirmed the effective separation of C3H6/C2H4(2:5) gas mixtures, yielding 6 N C2H4 (99.9999%) with the productivity of 65.7 L/kg. Theoretical calculations revealed that the separation mechanism involved molecular sieving effects and strong host-guest interactions toward C3H6, and was facilitated by hydrophobic interactions, hydrogen bonding, and suitable pore sizes.

Aliphatic ligands are often sidelined in the design of framework materials because their conformational flexibility can contribute to problems such as difficult crystallization, low porosity, and stability. Attempts to boost porosity by ligand elongation usually worsen these problems. Here we propose an expanded bioisosteric replacement (eBIS) concept capable of both scaling up and rigidifying aliphatic ligands. We demonstrate one example realized via linking two cyclohexyl rings in series, which restricts ligand flexibility through intramolecular non-covalent interactions providing an alternative to the π-conjugation-based rigidity. The resulting ligand displays consistent rigidity across multiple MOF platforms. On the pacs platform, it can realize extreme pore geometry with the highest hexagonal c/a ratio and new metal-cluster chemistry such as the first synthesis of nickel-titanium oxocluster. It can boost the BET surface area to as high as 2810 m2 g-1, likely the highest among aliphatic-dicarboxylate MOFs. Furthermore, it leads to possibly largest C2H6/C2H4 uptake differences (88 cm3 g-1, uptake ratio of 1.83, 273 K) among rigid MOFs, a desired property for C2H6-selective separation, which is confirmed by breakthrough experiments. The remarkably low adsorption enthalpies for C2H6 (14.7 kJ mol-1) and C2H4 (15.1 kJ mol-1) enables low-energy adsorbent regeneration benefitting practical separation.

Isoreticular chemistry conventionally tunes pore dimensions by varying linker length or manipulating substituents. While widely used, this strategy is constrained by the intrinsic chemistry of molecular building units, rendering certain size regimes and pore geometries inaccessible. Here, we establish coordination symmetry as an independent and powerful design variable for unit-cell compression in pore-partitioned acs (pacs) metal-organic frameworks. Replacement of D3h-symmetric tris(4-pyridyl) ligands with their C3h-symmetric tris(3-pyridyl) positional isomers induces controlled rotation of metal clusters without altering ligand size or framework topology. Curvature-encoded dicarboxylate linkers define a finite metal-cluster rotation window, within which donor-position symmetry selects distinct rotational states, producing systematic contraction along the hexagonal a/b directions and up to ∼15% reduction in unit-cell volume. Across multiple metal trimers and ligand combinations, this symmetry-controlled compression enhances framework stability and dramatically improves gas-separation performance. Importantly, the strategy enables simultaneous increases in C2H2 uptake and C2H2/CO2 or C2H2/C2H4 selectivity, overcoming the commonly observed trade-off between adsorption capacity and selectivity in porous material design. Ni3-24fdc-3tpt achieves record C2H2/CO2 and C2H2/C2H4 selectivities within the pacs family (42.35 and 25.14, respectively), together with high separation potentials and robust breakthrough performance. These results demonstrate that ligand-symmetry-driven metal-cluster rotation provides a general and predictive route to access compressed pore regimes beyond conventional linker-length modulation and expands the conceptual framework of isoreticular chemistry.

Trimer-based metal clusters are among the most compositionally versatile secondary building units in metal-organic frameworks (MOFs), but systematic control of heterometallic composition and framework charge within a structurally invariant platform remains challenging. Here, pore-space-partitioned acs (pacs) frameworks are employed as a model system to investigate compositional tunability at both the cluster and framework levels. Using 3,4-dimethylthieno[2,3-b]thiophene-2,5-dicarboxylate (dtc), a family of homo- and heterometallic pacs-MOFs based on Mg2+, Co2+, In3+, and V3+ trimers was synthesized. In the charge-complementary Mg/In system, variation of metal precursors and solvents enables broad tuning of the Mg/In ratio, while the large atomic-number contrast permits reliable occupancy refinement by single-crystal X-ray diffraction. The trimeric platform also supports an isostructural Co-, Co/V-, and V-based series in which framework charge changes from anionic to neutral and cationic without altering topology. Gas adsorption studies reveal charge-dependent C2H2/CO2 and C2H6/C2H4 separation behavior. Notably, neutral CoV-dtc-tpt exhibits a high C2H6 uptake of 164.8 cm3 g-1 and excellent inverse-selective C2H6/C2H4 separation, rivaling benchmark pacs materials. These results establish pacs-MOFs as a versatile platform for studying heterometallic assembly, framework-charge modulation, and structure-composition-property relationships.

Emerging as viable substitutes for lead halide perovskites in optoelectronic applications, 2D hybrid double perovskites exhibit low environmental impact, enhanced stability, and compelling optoelectronic traits. This study details the first chiral 2D Ag/Sb-based double perovskite ferroelectrics: (R/S-3AMP)2AgSbBr8 (where 3AMP = 3-(aminomethyl)-piperidine divalent cation), which exhibit a high Curie temperature of 440 K, an out-of-plane polarization of 3.8 & micro;C cm-2, and a strong second-harmonic generation circular dichroism (SHG-CD) response with an anisotropy factor up to 0.42. Moreover, the single-crystal-based X-ray detector exhibits an ultralow dark current of 0.14 nA cm-2, an ultralow detection limit of 3.78 nGyair s-1, a high sensitivity of 1187.13 & micro;C Gyair -1 cm-2, and excellent operational stability with no observable baseline drift, outperforming state-of-the-art perovskite single-crystal detectors. The superior X-ray detection performance is attributed to the synergistic effects of a suitable band gap, a unique 2D lattice, and a 1D electronic structure, as evidenced by density functional theory (DFT) calculations and crystal structure analysis. This study thus paves the way for next-generation intelligent sensing technologies that integrate detection, perception, and information processing.

ABSTRACT The exploration of 2D perovskites and chiral nonlinear optical materials has drawn significant interest due to their structural tunability and strong optical responses. However, the development of quasi‐2D perovskites has long been constrained by the limited choice of A‐site cations imposed by the traditional tolerance factor. In this study, we present a new 2D tri‐layered lead bromide perovskite (4AM) 4 Pb 3 Br 10 ( n = 3) with the general formula (A ′ ) 2 (A) n −1 M n X 3 n +1 , in which 4‐aminomonpholine cations (4AM) that act simultaneously as A‐site and spacer components, exhibiting an ultrahigh tolerance factor of 1.74—far beyond conventional limits. Crystallizing in the polar space group Cc , the compound shows an order‐disorder ferroelectric phase transition at 418 K. Interestingly it also exhibits notable chiral nonlinear optical properties, including strong second‐harmonic generation circular dichroism ( g SHG‐CD ≈ 0.63). This work breaks the classic tolerance factor constraint and opens a pathway for designing new chiral nonlinear optical materials in low‐dimensional perovskites.

Rashba-Dresselhaus (RD) spin splitting arising from spin-orbit coupling in spatial inversion asymmetric semiconductors is critical for realizing numerous advanced spintronic applications. However, modulating the RD spin splitting coefficient (αRD) is challenging due to the unclear structural-property relationship. Herein, inspired by highly distorted inorganic selenites containing stereochemically active lone pair (SCALP) electrons, we selected 4-aminomorpholine cation (4AM) containing SCALP electrons to synthesize a new two-dimensional (2D) ferroelectric semiconductor (4AM)2PbBr4, exhibiting a giant αRD of 2.377 eV Å with ΔERD = 126 meV and Δk0 = 0.106 Å-1 that differentiates circularly polarized light-excited carriers in the momentum space via spin-dependent optical transition selection rules with an asymmetric factor of 0.65. A geometric structure-property relationship study reveals that incorporating SCALP into the organic cations enhances their net polarity and induces substantial distortions within the inorganic sublattices that enhance the αRD. This work reveals the regulatory mechanism of organic cations on distortion of inorganic octahedron and provides a new approach for efficient synthesis and rapid screening of 2D ferroelectric semiconductors with large αRD.

Reference electrodes are essential for meaningful electrochemical measurements but face significant challenges in miniaturization and long-term stable potential. Conventional commercial reference electrodes, which rely on ion migration across porous frits, suffer from electrolyte leakage, potential drift, and limited scalability to micro dimensions. Quasi-reference electrodes lack a thermodynamically defined interface, exhibiting polarization-sensitive potentials that drift with experimental conditions, compromising their reliability for rigorous quantitative analysis. Therefore, a miniaturized reference electrode capable of stable potential output is critical for techniques like scanning electrochemical cell microscopy (SECCM), where accuracy and spatial resolution depend on electrode robustness. Herein, we report a facile and reproducible strategy to fabricate a nanopipette reference electrode (NPRE) leveraging nanoscale ion transport. This architecture replaces conventional glass bodies and fritted junctions with a monolithic pulled capillary structure, integrating a nanoscale terminal pore that inherently minimizes electrolyte leakage. The NPRE demonstrates excellent potential stability (>24 h) in both aqueous and organic media, underscoring its robustness across distinct chemical environments. Successful integration of NPRE with SECCM enables precise nanoscale electrochemical measurements, effectively overcoming the inherent limitations of conventional systems and providing an ideal platform for high-resolution studies in complex physiological or materials environments.

The development of a theoretical framework typically proceeds from idealized cases toward increasingly nonideal situations. Over the past decade, pore-space partitioning (PSP) has been predominantly explored in high-symmetry systems based on trimers at the highest D3h symmetry. Extending PSP toward a more general theoretical framework would encompass a purposeful reduction of the symmetry of building blocks or crystal symmetry. However, the design of partitioning strategies is more challenging in lower-symmetry situations. Herein, we report several new types of PSP-enabled metal-organic framework (MOF) platforms featuring ligand-triggered lower building-block symmetry or interpenetration-triggered lower crystal symmetry (even if the building-block symmetry is at the maximum). This expansion of PSP is realized through a new conceptual strategy termed retro-PSP, which enables the construction of partitioning ligands with adaptable symmetry and the discovery of tripyridyl ligands with C3h symmetry as partitioning ligands. In addition to a new form of partitioning mode for acs net (t2-pacs) via partitioning of a trigonal-bipyramidal cage (instead of previously observed partitioning of straight channels) and the hierarchical partition in 2- and 3-fold interpenetrating acs nets (x2-pacs and x3-pacs), we have also created the partitioned pcu (pcup) and partitioned nia (pnia) systems. This work results not only in the discovery of new topologies not known before, but also the experimental realization of topologies that had previously existed only as theoretical predictions. Collectively, this work establishes retro-PSP as a generalizable approach for extending PSP to include either more partition modes or more MOF platforms, resulting in new PSP-enabled materials with enhanced stability and tunable gas adsorption properties.

Trimer-based metal clusters are among the most compositionally versatile secondary building units in metal-organic frameworks (MOFs), but systematic control of heterometallic composition and framework charge within a structurally invariant platform remains challenging. Here, pore-space-partitioned acs (pacs) frameworks are employed as a model system to investigate compositional tunability at both the cluster and framework levels. Using 3,4-dimethylthieno[2,3-b]thiophene-2,5-dicarboxylate (dtc), a family of homo- and heterometallic pacs-MOFs based on Mg2+, Co2+, In3+, and V3+ trimers was synthesized. In the charge-complementary Mg/In system, variation of metal precursors and solvents enables broad tuning of the Mg/In ratio, while the large atomic-number contrast permits reliable occupancy refinement by single-crystal X-ray diffraction. The trimeric platform also supports an isostructural Co-, Co/V-, and V-based series in which framework charge changes from anionic to neutral and cationic without altering topology. Gas adsorption studies reveal charge-dependent C2H2/CO2 and C2H6/C2H4 separation behavior. Notably, neutral CoV-dtc-tpt exhibits a high C2H6 uptake of 164.8 cm3 g-1 and excellent inverse-selective C2H6/C2H4 separation, rivaling benchmark pacs materials. These results establish pacs-MOFs as a versatile platform for studying heterometallic assembly, framework-charge modulation, and structure-composition-property relationships.

3D hybrid lead halide perovskites exhibit exceptional optoelectronic properties but face inherent limitations in achieving stable ferroelectricity due to dynamic disorder and ion migration. Recent breakthroughs in lattice-expanded 3D analogs (A'Pb2X6) overcome the limitation via substitution of isolated [PbX6] octahedra with edge-shared [Pb2X10] dimer units, thereby expanding the framework and enabling cation-based property regulation. Herein, we construct a new 3D lead bromide ferroelectric semiconductor (M(2)pda)Pb2Br6 (M(2)pda is N,N '-dimethyl-1,3-propanediammonium) by bromine-substitution strategy, featuring a Curie temperature of 263 K and spontaneous polarization of 0.5 mu C/cm(2). The crystal material demonstrates a direct bandgap of 2.83 eV and achieves efficient linearly polarized light (LPL) detection at 405 nm, with an on/off current ratio >1.7 x 10(2) and high photocurrent anisotropy factor (omega = 1.32). This work provides new guidance and reference for the design and synthesis of 3D perovskite ferroelectrics.

Expanding the scope of isoreticular chemistry to include chiral ligands remains a fundamental challenge, particularly for high-symmetry framework topologies that generally favor symmetry matching between building blocks and the crystallographic sites they occupy. Here, we demonstrate that the partitioned acs (pacs) platform can accommodate a chiral dicarboxylate ligand, (1R,3S)-(+)-camphoric acid (d-cam), representing the first pacs MOF constructed from a chiral L1 ligand. The successful assembly of the framework is enabled by the cooperative structure-directing effects of a tripyridyl pore-partitioning ligand and heterometallic Co/In trinuclear clusters, which collectively enforce alignment of ligand coordination vectors while permitting subtle charge and size tunability through variable Co2+/In3+ ratios within the trimers. Structural analysis reveals that the framework preserves the characteristic pacs architecture despite geometric distortion arising from the stereochemical features and low symmetry of the ligand. These results suggest that geometric mismatch is redistributed throughout the framework through cooperative distortion of ligand orientation, cage geometry, and trimer coordination environment. Gas sorption studies reveal preferential adsorption of C2H2 over CO2, while breakthrough experiments demonstrate stable C2H2/CO2 separation over multiple cycles. More broadly, this work suggests that cooperative multimodule assembly can relax classical symmetry-matching constraints in isoreticular chemistry.

Advancement of next-generation information technologies is driving the increasing integration of millimeter-wave and terahertz (THz) communication, detection, and artificial intelligence technologies, thereby creating a demand for multifunctional absorbing materials to address complex electromagnetic interference. In this study, a flexible WPU-MXene@FC composite fabric with ultra-broadband absorption, superhydrophobicity, and excellent durability is developed. The base fabric (FC) is modified via surface plasma treatment to introduce positively charged active sites on fibers. Driven by electrostatic interaction, negatively charged MXene is self-assembled with modified FC. The electrostatic interactions process induces a "nest-like" structure on fibers, building construct MXene multiple loss paths. Waterborne polyurethane (WPU) is finally coated to endow the FC with MXene oxidation protection, superhydrophobicity, and stability. Results show that a 1.8 mm-thick WPU-MXene@FC achieves an effective absorption bandwidth spanning 25.3-1200 GHz. Within 0.2-1.0 THz, the reflection loss (RL) value is below -30 dB, reaching a minimum of -45.2 dB. After 500 bending cycles, its RL remains below -30 dB. The WPU-MXene@FC exhibits superhydrophobicity (contact angle 151.3°, sliding angle 1.2°), excellent air permeability, and flexibility. This multifunctional FC has important applications in wearable devices, communications, and provides strong support for the development of lightweight stealth structures and flexible electromagnetic camouflage.

Hybrid metal halides (HMPs) have attracted considerable attention from researchers exploring broad-band luminescence materials due to their low cost and excellent photophysical properties. Although lots of structures have been done...

Tissue regeneration during bone defect repair is regulated by the energy metabolism of macrophages. Abnormal energy metabolism can negatively affect bone repair in pathological conditions. A promising strategy involves developing biomaterials that regulate macrophage energy metabolism to coordinate immune response and bone regeneration. In this study, hollow mesoporous MnO2, known for its excellent reactive oxygen species (ROS) scavenging and drug-loading abilities, was loaded with dexamethasone. This was followed by electrostatic selfassembly using chitosan coating to create nanogels (Alg-MD@CS). In vitro experiments showed that the nanogel effectively scavenged excess ROS, restored mitochondrial function, and reduced the levels of inflammatory factors. It downregulated glycolysis by inhibiting the ERK/HIF-1 alpha/GLUT1 pathway, facilitating the M1-to-M2 phenotype switch to promote an anti-inflammatory and pro-regenerative ecological environment. In vivo experiments confirmed these findings. The nanogel reduced ROS levels in rats, reshaped the local immune microenvironment, and promoted bone regeneration. In summary, we developed a multifunctional nanogel for bone defect repair and demonstrated the significance and feasibility of reverse reprogramming by regulating the energy metabolism of macrophages during bone regeneration.

Hybrid halide perovskites (HHPs) have garnered significant attention among researchers exploring nonlinear optical (NLO) materials due to their robust structural designability and impressive photophysical characteristics. Despite considerable efforts in optimizing their chemical compositions and structural dimensions, the role of large distorted [AgX6](5-) octahedra in double perovskites on the design of HHPs materials with strong second harmonic generation (SHG) effect is underestimated or even overlooked. In the study, a double perovskite structure (DFPD)(4)AgBiBr8H2O (DFPD = 3,3-difluoropiperidinium), is obtained with significant polar distortion of [AgBr6](5-) octahedra, which shows a remarkable SHG intensity of 13.0 x KDP, a moderate birefringence of 0.095@532 nm, a high laser-induced damage threshold (LIDT) value of 241.3 MW cm(-2), and an ultra-long structural stability (>12 months) at 60% relative humidity air atmosphere. The research underscores the advantages of utilizing double perovskites with highly distorted [AgBr6](5-) octahedra in the development of HHPs with excellent SHG response, and provides a novel insight into the design of advanced NLO materials.

An emerging direction in the design of crystalline porous materials is the application of bioisosteric replacement strategy that replaces benzene ring with an aliphatic core; however, maintaining isoreticular chemistry upon such replacement is elusive. While bicyclic cores have been employed for this purpose, few studies are known that use spiro ligands for designing metal-organic frameworks for gas separation applications. As a benzene bioisostere, spiro ligands are more challenging than other bioisosteres because they are more flexible and deviate significantly from that of para-benzene-based ligands. In this work, we show that the use of a pore-space-partition strategy generates a multimodule system in which it is possible to exert a high level of control over the positioning, orientation, and alignment of carboxylate groups in a spiro ligand. Here, we report a family of isoreticular MOFs on a partitioned acs (pacs) structure with spiro[3.3]heptane-2,6-dicarboxylic acid as the framework-forming module, together with three different pore-partition modules based on tripyridyl ligands. The isoreticular chemistry can be extended to both homometallic (Fe) and heterometallic (CoV and CoFe) compositions. These materials exhibit excellent sorption properties such as high uptake capacity for CO2 (61.9 cm3/g) and small hydrocarbon gases (e.g., 116.3 cm3/g for C2H2 and 101.4 cm3/g for C2H4), inverse C2H6/C2H4 selectivity, and promising separation performance for C2H2/CO2 (selectivity up to 5.5), C3H8/CH4 (selectivity up to 279), and C2H6/CH4 (selectivity up to 22.7) gas mixtures.

Polarization-sensitive photodetectors enable effective information transmission in the field of optical communications by identifying the polarization state of linearly polarized light (LPL). Dual-polarity photodetectors are capable of generating controllable photocurrent signals with discrepancies of polarities at multiple levels. The combination of dual-polarity photoresponse and polarization-sensitive photodetection may offer a potential solution for encrypting polarization information. Here, dual-polarity polarization-sensitive photodetection is successfully achieved in a bilayer hybrid perovskite ferroelectric (2TMA)2(MA)Pb2I7 (2TM-2; 2TMA = 2-thiophenemethylammonium, MA = methylammonium). The alteration of the ferroelectric polarization direction results in corresponding changes in the anisotropic photoresponse driven by the bulk photovoltaic effect. The photocurrent anisotropy ratio omega (17.7) of 2TM-2 is the largest among the reported lead iodide perovskite single crystal devices. Specifically, an encrypted LPL communication model is proposed based on this switchable dual-polarity polarization-sensitive photosensitive detector and simulates the encrypted transmission process of capital letter "LPL" signals. This work offers new insights into the electrical control of polarization-sensitive photoresponse in hybrid perovskite ferroelectrics and is expected to have a transformative impact on the field of secure communication technology.

Reduction of melting temperature (Tm) stands as a pivotal challenge in advancing the applications of two-dimensional metal halide perovskites (2D MHPs). Herein, we employ an alloying strategy to effectively depress the Tm, which has been systematically investigated through a case study involving the synthesis of 1x21-x and 1x31-x mixed hybrid metal halide systems (1 = (MIPA)2PbI4, 2 = (MIPTA)2PbI4, 3 = (GABA)2PbI4, MIPA = N-methyliodopropylammonium, MIPTA = N-methyliodopentylammonium, and GABA = 4-ammoniumbutyric acid cation; x = 0-1). The Tm and enthalpy changes of the hybrid systems exhibit concentration-dependent variation as characteristics of partial solid solution binary mixtures. Notably, 10.6020.40 exhibits a record-low Tm of 60 degrees C among 2D MHPs. The underlying mechanism of eutectic formation is elucidated through the critical role of mixing entropy in reducing the Gibbs free energy change during melting. The melt-processing capability and glass-forming ability of the mixed compounds are verified. The applicability of this strategy is further validated by the 10.5530.45 system exhibiting a Tm of 80 degrees C. This mixing-entropy-driven approach provides both a practical pathway for Tm reduction in 2D MHPs and insights into the design of partial solid-solution binary mixture systems.