Hydrogen-bonded organic frameworks (HOFs) are promising porous materials, yet their development is hindered by an inherent trade-off between structural stability and functional site accessibility. Conventional stabilization strategies relying on extensive π-π stacking inevitably shield aromatic surfaces, compromising adsorption performance. Herein, we report a synergistic design strategy that integrates high hydrogen-bonding connectivity with inherently nonplanar molecular conformations to overcome this challenge. The strategically designed tetraisophthalate linker, featuring a hexamethylbiphenyl core, adopts a nonplanar conformation that suppresses extended π-π stacking, while its eight carboxylic acid groups form a dense hydrogen-bonded network ensuring framework robustness. The resulting HOF-ZJNU-10 exhibits a high BET surface area (2500 m2 g-1), exceptional stability, and crucially, fully accessible aromatic surfaces lining the pore channels. This unique combination enables outstanding methanol-to-olefins (MTO) product purification, delivering polymer-grade ethylene and propylene with record-high productivity. This work establishes a general blueprint for decoupling stability from functional site masking in HOFs.

Efficient separation of propylene from propane is a critical yet challenging industrial process. While rigid molecular sieves offer ideal selectivity, their narrow nanopores inherently constrain adsorption capacity and diffusion kinetics due to compromised thermodynamic-kinetic trade-offs. To address this, we report ZSTU-10, a molecular sieve constructed via structure-directing agents. Uniquely, ZSTU-10 features localized sieving gates for selective guest admission, expansive diffusion channels for rapid transport, and central pore cavities for high-capacity storage. This gate-channel-cavity architecture enables the precise exclusion of propane while facilitating the dense packing and fast diffusion of propylene, achieving simultaneous thermodynamic-kinetics optimization in molecular sieving. Static adsorption experiments demonstrate an exceptional propylene uptake (97.7 cm3 cm-3) at 298 K and 1 bar. Time-dependent uptake kinetics revealed a propylene diffusion coefficient (4.29 × 10-9 cm2 s-1) in ZSTU-10 surpassing benchmarks by two orders of magnitude. Dynamic breakthrough experiments demonstrate that ZSTU-10 produces high-purity propylene (99.1%) with a productivity of 37.5 L kg-1 in a single adsorption-desorption cycle.

A critical bottleneck in photocatalytic H2O2 production lies not only in the severe non-radiative energy losses incurred from enhancing light absorption, but also in a fundamental proton-electron kinetic imbalance. Here we introduce a light-heat-proton coupling strategy that harnesses the dissipated photothermal energy to activate proton dissociation from carboxylic acids, thereby creating a productive driving force for redox catalysis. A hydrogen-bonded organic framework (HOF-FJU-200) incorporating mixed-valence Fe2+/Fe3+ clusters is constructed via a metalloligand approach. The intervalence charge transfer transitions within these clusters generate strong photothermal conversion while extending light absorption to the NIR-II region ( ~ 2500 nm). The resulting thermal energy activates proton dissociation from unpaired carboxylic acid groups, synchronizing proton release with photoinduced electron transfer. This cooperative mechanism effectively channels non-radiative heat into catalytic function, achieving an H2O2 production rate of 10657 μmol·g-1·h-1 without sacrificial agents. By directly coupling light, heat, and proton dynamics within a single framework, this work establishes a general paradigm for utilizing non-radiative energy to regulate proton-driven photocatalytic reactions.

Crystalline porous materials are orchestrating a paradigm shift in precision medicine. Prototypical metal-organic frameworks (MOFs) define the realm of "pore chemistry" by leveraging compact, thermodynamically stable coordination backbones to construct chemically programmable microenvironments. In stark contrast, hydrogen-bonded organic frameworks (HOFs) introduce an orthogonal paradigm. This new frontier, "pore mechanics", is governed by relatively loose, reversible non-covalent networks. Rather than framing this transition as a linear structural evolution, this review critically conceptualizes it as a fundamental trade-off in material design. We dissect the "chemical gating" strategies, detailing how atomic-level surface engineering and post-synthetic modification of metal-organic frameworks toward applications create smart valves responsive to endogenous biochemical gradients. Subsequently, we delineate the unique behaviours of HOFs, distinguishing between thermodynamically driven "induced-fit" mechanisms-facilitated by the pre-organization of the lattice and an energy barrier descent-and true exogenous mechanochemical scission (e.g., ultrasound-triggered dissociation). By critically contrasting the thermodynamic robustness of MOFs with the kinetic lability of HOFs, we confront their respective translational barriers, weighing the inorganic persistence of MOFs against the severe hydrophobic aggregation risks of free HOF monomers. Emphasizing rigorously controlled comparisons over simple superposition, we establish a rational selection roadmap for clinical translation. Finally, we highlight the frontier of MOF-HOF heterostructures, envisioning a dual logic-gated (AND-gate) delivery model. This architecture synergizes chemical robustness with mechanical intelligence, challenging the field to overcome the formidable spatiotemporal barriers of deep-tissue biological delivery.

Direct acquisition of polymer-grade ethylene from ethane/ethylene (C2H6/C2H4) mixtures remains a formidable industrial challenge. While hydrogen-bonded organic frameworks (HOFs) offer a promising low-energy platform, their inherent structural flexibility often compromises stability and separation performance. Herein, we introduce a dual-purpose "Z-pinning" strategy to construct a robust HOF, HOF-FJU-202, for highly efficient reversed C2H4/C2H6 separation. Anthracenyl motifs serve as molecular "Z-pins" oriented perpendicular to hydrogen-bonded layers, bridging them via edge-to-face π-interactions. This significantly enhances out-of-plane stability and chemical/thermal robustness. Simultaneously, these channel-lining anthracenyl groups act as π-rich sites preferentially binding C2H6 via multiple C─H···π interactions. This synergistic architecture delivers polymer-grade C2H4 with a productivity of 11.2 L/kg from equimolar mixtures and a record 25.5 L/kg from 10/90 lean mixtures, setting a new benchmark for HOF materials. Furthermore, HOF-FJU-202 is readily synthesized on a 20 g scale and processed into robust granules with a compressive strength of 32.1 N, while showing negligible performance loss, underscoring its practical potential. Comprehensive crystallographic, spectroscopic, and computational analyses confirm that the anthracenyl Z-pins are critical for both maintaining structural integrity and facilitating preferential C2H6 capture. These findings demonstrate that integrating mechanical reinforcement with functional recognition sites is a potent strategy for developing stable, task-specific porous materials.

Supramolecular macrocycles, despite their ubiquity in molecular recognition, have remained largely unexplored in photocatalysis due to their intrinsic lack of continuous pi-conjugation and inefficient charge-carrier separation. Here, we report a conformational engineering strategy to integrate dynamic B <- N dative bonds into highly active photocatalytic macrocyclic architectures. By simply switching the boronate linker from meta to para geometry, we control the rotational freedom of B <- N bonds to yield two isomeric frameworks-twisted BNF-80 and planar BNF-81-with well-defined supramolecular macrocyclic building units, as unequivocally confirmed by single-crystal X-ray diffraction. The planarized conformation of BNF-81 enforces extended pi-conjugation and continuous pi-pi stacking, leading to markedly enhanced charge separation efficiency and charge transfer. As a result, BNF-81 achieves an outstanding photocatalytic H2O2 production rate of 4275 mu mol & centerdot;g-1 & centerdot;h-1 under visible light in pure water without any sacrificial agent, outperforming previously reported B <- N-based photocatalysts. This work establishes linker conformation driven control as a powerful design principle, unlocking the latent photocatalytic potential of supramolecular macrocycles and opening a new avenue for developing efficient metal-free photocatalysts.

ABSTRACT Achieving simultaneously high ion permselectivity and chemical robustness in concentrated electrolytes remains a central challenge for membrane‐based technologies, because strong electrostatic screening suppresses charge‐based exclusion while corrosive acids and bases accelerate material degradation. Here we report a molecular strategy to construct robust linkage‐encoded covalent organic framework (COF) membranes in which short‐range ion‐framework interactions are embedded directly within fully conjugated enaminone linkages lining vertically aligned nanochannels. By holding framework topology and pore architecture constant while varying only the linkage chemistry, we show that the linkage microenvironment governs ion selectivity, transport efficiency, and chemical stability. Periodic enaminone motifs create persistent coordination environments and hydrogen‐bond networks that remain effective at high ionic strength, enabling ultrafast proton transport exceeding Nafion 212 by more than fivefold. The membrane preserves crystallinity and pore alignment and maintains performance after exposure to 12 M H 2 SO 4 at 110°C and under concentrated alkaline conditions. To demonstrate performance under extreme conditions, it delivers a peak osmotic power density of 2422.9 W m −2 under a 12 M || 0.01 M H 2 SO 4 gradient while maintaining stable continuous operation. This linkage‐encoding paradigm provides a general route to ion‐selective, chemically resilient membranes for reliable ion transport and electrochemical technologies operating in chemically extreme electrolytes.

ABSTRACT The photocatalytic synthesis of hydrogen peroxide (H 2 O 2 ) from O 2 and H 2 O represents a sustainable alternative to the energy‐intensive anthraquinone process. However, achieving efficient photocatalysis requires precise control over structure–activity relationships, which remains a significant challenge. Herein, we report a molecular engineering strategy that leverages precise tuning of intermolecular π‐stacking in three single‐crystalline dative B←N frameworks (BNF‐75, ‐76, and ‐77). By systematically modulating the planarity of the B‐acceptors, we achieved a progressive decrease in the root‐mean‐square deviation (RMSD) of the B‐acceptors from 0.463 Å in BNF‐75 to 0.201 Å in BNF‐77. The BNF‐77 exhibits broadened visible‐light absorption, enhanced charge separation and transport, and an outstanding H 2 O 2 production rate of 5684.6 µmol·g −1 ·h −1 under visible light without sacrificial agents or metal cocatalysts (λ > 420 nm). Simple mechanical grinding for particle‐size reduction further elevates the rate to a remarkable 9451.0 µmol·g −1 ·h −1 , positioning BNF‐77 among the top‐performing crystalline photocatalysts based on dative B←N bonds. Integrated mechanistic studies reveal a synergistic mechanism: the dative B←N bond extends light harvesting and promotes charge separation, while the engineered tight π‐stacking constructs efficient charge‐transport highways and facilitates the two‐electron oxygen reduction reaction (ORR) pathway, with superoxide radicals (•O 2 − ) as the key intermediate.

Atomically precise coinage metal nanoclusters possess well-defined structures and distinctive optoelectronic properties. However, their assembly through weak van der Waals interactions often results in inefficient charge migration and rapid electron-hole recombination. Hydrogen-bonded organic frameworks (HOFs) offer an alternative strategy to integrate functional clusters into ordered crystalline materials while preserving molecular isolation. Herein, we report the first example of coinage-metal-cluster-based donor-acceptor (D-A) heterojunction engineered into a HOF. A tailored Ag6 cluster serves as the electron-rich donor, and 4,4'-bipyridine (BPY) acts as the electron-deficient acceptor. Directional N─H···N hydrogen bonds guide the assembly into a crystalline Ag6-HOF, which retains the intrinsic structure of the Ag6 clusters while creating hydrogen-bonded channels for enhanced inter-cluster charge transport. Photoelectrochemical studies and density functional theory calculations reveal an S-scheme heterojunction, with the highest occupied molecular orbital (HOMO) localized on the Ag6 cluster and the lowest unoccupied molecular orbital (LUMO) on the BPY linker. This electronic configuration promotes spatial charge separation, extends visible-light absorption, and significantly boosts photocatalytic H2O2 production compared to the individual components. The work demonstrates hydrogen-bond-directed assembly as a precise and versatile approach to design cluster-based heterojunctional materials with tunable electronic structures and enhanced photocatalytic performance.

Abstract Three one-dimensional porous coordination polymers (PCPs) based on Cu2(OAc)4 paddle-wheel clusters were synthesized by using pyridyl ligands with distinct coordination geometries, including linear 1,4-di(4-pyridyl)benzene (DPB) and bent triazole-based ligands 3,5-bis(4-pyridyl)-1,2,4-triazole (HBPT) and 4-amino-3,5-bis(4-pyridyl)-1,2,4-triazole (HABPT). Single-crystal X-ray diffraction (SCXRD) reveals that all three compounds share a common [Cu2(OAc)4(L)] stoichiometry and paddle-wheel motif but assemble into different chain conformations and three-dimensional packings depending on ligand geometry and torsional flexibility. Gas adsorption measurements combined with PXRD analyses indicate irreversible densification of the DPB-based PCP upon desolvation, resulting in negligible accessible porosity. In contrast, the HABPT-based analogue exhibits suppressed gas uptake despite retaining crystallinity, suggesting vacuum-induced framework contraction. Among them, the HBPT-based analogue retains permanent porosity and exhibits a moderate thermodynamic preference for C2H2 over CO2, as supported by adsorption measurements, Qst analysis, IAST calculations, and molecular simulations.

The purification of ethylene (C2H4) from ternary C2H2/CO2/C2H4 mixtures remains a critical yet challenging process in the petrochemical industry. Traditional physisorption methods integrating even advanced metal-organic frameworks (MOFs) often suffer from insufficient selectivity and/or impractical regeneration. Herein, we report a kinetic separation strategy using ZNU-16, a MOF with tunable crystal sizes, to selectively exclude C2H4 by leveraging its slower kinetics in larger crystals (ZNU-16-L). While conventional approaches minimize crystal size to enhance adsorption kinetics, ZNU-16-L intentionally retards C2H4 diffusion, achieving near-zero C2H4 uptake (2.9 cm3 g-1) while retaining high capacities for C2H2 (61.7 cm3 g-1) and CO2 (30.8 cm3 g-1) at 298 K and 1 bar. Breakthrough experiments demonstrate one-step production of >= 99.999% pure C2H4 with a productivity of 42.6-80.0 L/kg. Density functional theory calculations revealed the preferential interactions of C2H2 and CO2 via fluorine-mediated interactions, implying relatively moderate energies that enable mild regeneration. Notably, ZNU-16-L maintains separation performance under humid conditions and across multiple cycles, highlighting its industrial viability. This work demonstrates that crystal-size modulation in tandem with pore engineering, offers a sustainable pathway to address the growing global demand for high-purity ethylene.

The efficient separation of C2H2 from C2H2/CO2 and C2H2/C2H4 mixtures is essential for the preparation of high-purity C2H2 and C2H4, but challenged by the trade-off between the capacity and selectivity. In this work, we report a node guided pore engineering strategy in carborane-based metal-organic frameworks (MOFs), leading to the partitioned dual cage system in Co-CB-HPBTA in contrast to its analogue Zn-CB-HPBTA with one-dimensional channels. This structural evolution endows Co-CB-HPBTA with a high C2H2 adsorption capacity of 103.2 cm3/g (4.61 mmol/g) at 298 K and 1 bar, along with superior selectivity for C2H2/CO2 (10.6) and C2H2/C2H4 (13.3). Breakthrough experiments confirm its excellent separation performance for both mixtures under varied conditions, demonstrating efficient recovery of high-purity C2H2 and C2H4 with remarkable cyclic stability and humidity tolerance. The separation mechanism is elucidated by DFT calculations and in situ single-crystal-ray diffraction, which reveal enhanced binding interactions within the partitioned cages through multiple van der Waals contacts, rationalizing the high selectivity.

Wound healing is significantly impeded by bacterial infection and excessive inflammation, exacerbated by antibiotic resistance and the accumulation of excessive reactive oxygen species (ROS). To address this challenge, for the first time, we engineered a hydrogen-bonded organic framework (HOF)-based pH-adaptive nanocomposite CaO2@HOF-Fe by integrating a pH-responsive H2O2-generating capability of CaO2 with multienzymatic activities of a ferriporphyrin-based hydrogen-bonded organic framework (HOF-Fe). In the weakly acidic microenvironment of infected wounds, CaO2 gradually releases H2O2, which is subsequently converted into highly toxic hydroxyl radicals (•OH) by HOF-Fe with enhanced peroxidase (POD)-like activity, enabling on-demand antimicrobial chemodynamic therapy (CDT); in vitro studies demonstrated that this nanocomposite completely eradicated Staphylococcus aureus and methicillin-resistant S. aureus at a very low concentration of 0.9 and 1.8 μg mL-1, respectively. Under neutral physiological pH, HOF-Fe exhibits superoxide dismutase (SOD)- and catalase (CAT)-like activities, effectively scavenging excessive ROS and thereby mitigating inflammation. Furthermore, the CAT-like activity of HOF-Fe facilitates oxygen molecular generation from overexpressed H2O2, alleviating hypoxia and promoting angiogenesis. By concurrently addressing bacterial burden and excessive inflammation while also facilitating ROS elimination and oxygen generation, the CaO2@HOF-Fe nanocomposite significantly accelerates the infected wound healing, offering a promising, resistance-mitigating approach for clinical translation in infected wound management.

Photoenzymatic reduction of CO2 to formate is a promising strategy for carbon valorization, yet its efficiency is still limited by inefficient energy and mass transport. Here, we design a series of isostructural hydrogen-bonded organic frameworks (HOFs) that establish confinement effects to promote photocatalytic NADH regeneration and the subsequent NADH-dependent enzymatic CO2-to-formate reduction. We demonstrate that spatial confinement within the framework channels localizes exciton migration to nanoscale domains and promotes interfacial dissociation. Additionally, Rh-induced electronic-structure modulation enables ultrafast electron transfer, while the intrinsic hydrogen-bond network furnishes directional proton conduction to NAD+. These synergistic regulations afford a photocatalytic NADH regeneration efficiency of 99.8% with a record apparent quantum efficiency of 32.8%, and drive formate production at a rate of 3020 μmol g-1 h-1 with 100% selectivity─the highest rate reported to date for all light-driven systems in water. The HOF-based catalyst retains 86.3% of its initial activity over five cycles, highlighting its robustness. This work offers mechanistic insight into how microenvironment engineering within HOF architectures regulates energy and mass transport in photoenzymatic catalysis, paving the way for the rational design of advanced hybrid catalytic systems.

Mesoporous materials represent an important class of porous materials; however, it remains a great challenge to systematically synthesize hybrid single-crystalline mesoporous frameworks merging metal-organic and hydrogen-bonded organic networks. Herein, we report a hybrid merged-net strategy that integrates a supramolecular hydrogen-bonded organic network with a single-crystalline mesoporous metal-organic framework (MOF), significantly enhancing structural robustness without sacrificing intrinsic mesoporosity. The assembly of pyridine-containing carboxylate linkers and iron-containing trinuclear clusters affords M-PPB featuring the (6,6)-connected 62T44 net, in which directional O─H⋯N hydrogen bonds between adjacent linkers form a one-dimensional hydrogen-bonded network. In contrast to the unstable parent (4,6)-connected stp-MOF, M-PPB-merging metal-organic and hydrogen-bonded organic networks-exhibits enhanced robustness and achieves full porosity, displaying a pore volume of 1.58 cm3 g- 1. We further apply an isoreticular expansion strategy to synthesize extended MOFs-M-PPPB-containing mesopores of about 4.2 nm and exhibiting a pore volume of up to 2.77 cm3 g- 1. On account of its ultrahigh porosity, M-PPPB exhibits a methane uptake of 1.047 g g- 1 at 159 K and 10 bar, nearly twice that of M-PPB, while its hydrogen uptake at 77 K and 100 bar increases by about 50%.

Ideal separators for rechargeable lithium-sulfur (Li-S) batteries should facilitate Faradaic reactions near the electrode surface while mitigating the shuttle effect. However, conventional separator materials often exhibit sluggish Li+ migration rates and reaction kinetics due to their high Li+ desolvation energy and diffusion resistance. Investigating the Li+ transport mechanism within separators and elucidating Li+ desolvation process remains a significant challenge. Herein, we systematically elucidated the desolvation capability of Metal-organic frameworks (MOF) channels in Li+ diffusion process by MOF pore engineering. It is concluded that negative charge sites weaken the interaction between Li+ and solvent molecules, and smaller pore sizes reduce the distance between Li-solvent complexes and negatively charged sites, which further improve the desolvation of Li+. The desolvated Li+ subsequently participates rapidly in the polysulfide conversion process, thereby enhancing sulfur redox kinetics and keeping the concentration of polysulfides in the electrolyte remains at a lower level. This enables Li-S batteries to exhibit excellent electrochemical performance under high current densities and high sulfur contents. This work provides valuable new insights into controlling the Li+ solvation structure, highlight the significant potential of MOF-based separators in Li-S batteries.

The photocatalytic synthesis of hydrogen peroxide (H2O2) from O2 and H2O represents a sustainable alternative to the energy-intensive anthraquinone process. However, achieving efficient photocatalysis requires precise control over structure-activity relationships, which remains a significant challenge. Herein, we report a molecular engineering strategy that leverages precise tuning of intermolecular π-stacking in three single-crystalline dative B←N frameworks (BNF-75, -76, and -77). By systematically modulating the planarity of the B-acceptors, we achieved a progressive decrease in the root-mean-square deviation (RMSD) of the B-acceptors from 0.463 Å in BNF-75 to 0.201 Å in BNF-77. The BNF-77 exhibits broadened visible-light absorption, enhanced charge separation and transport, and an outstanding H2O2 production rate of 5684.6 µmol·g-1·h-1 under visible light without sacrificial agents or metal cocatalysts (λ > 420 nm). Simple mechanical grinding for particle-size reduction further elevates the rate to a remarkable 9451.0 µmol·g-1·h-1, positioning BNF-77 among the top-performing crystalline photocatalysts based on dative B←N bonds. Integrated mechanistic studies reveal a synergistic mechanism: the dative B←N bond extends light harvesting and promotes charge separation, while the engineered tight π-stacking constructs efficient charge-transport highways and facilitates the two-electron oxygen reduction reaction (ORR) pathway, with superoxide radicals (•O2 -) as the key intermediate.

The efficiency of electrocatalytic CO2 reduction (ECR) is largely governed by the adsorption of CO2, a step often accompanied by pre-activation via molecular bending and electron redistribution before the first electron transfer occurs. However, the explicit correlation between the extent of CO2 pre-activation and the resultant reaction performance remains elusive due to the lack of direct structural evidence. Herein, we employ two In-MOFs, FJU-350 and FJU-351, as crystalline model catalysts to visualize distinct CO2 pre-activation configurations and unravel their critical role in ECR. FJU-350 exhibits superior ECR performance with FEformate of 90.9% at -1.4 V (vs. RHE), outperforming FJU-351 (88.6% at -1.6 V). Single-crystal X-ray diffraction analyses indicate that this 200 mV efficiency gain is the consequence of their distinct structural microenvironments. FJU-350 features a polarized carboxyl-oxygen site, stabilizing a uniquely bent CO2 species (127.2°) via single-site interaction, indicative of pronounced pre-activation. Theoretical calculations confirm that the highly distorted configuration facilitates charge transfer and lowers the energy barrier. In contrast, FJU-351 lacks such a directed site, accommodating near-linear CO2 (≥153.3°) via delocalized π-interactions. This work reveals a correlation between the pre-activated CO2 configuration and its electroreduction performance, providing a strategic foundation for designing efficient catalysts through precise micro-environment engineering.

The selective oxidation of ethylene (C2H4) and propylene (C3H6) offers the most important route for preparing a variety of platform chemicals. However, current industrial synthesis still relies on diversified thermo-oxidation methods, resulting in complex, inefficient, and high-cost production. Herein, we report a redox heterometallic cluster (TiIV16MnII4) catalyst capable of achieving unprecedented cascade oxidation of C2H4 and C3H6 to divergent products in a simple photoassisted electrochemical system. In situ characterizations combined with theoretical calculations disclose that under photoelectrochemical (PEC) operation, different electron transfer processes between the peripheral MnII centers and the internal {TiIV16O22} "electron reservoir" produce multiple active oxidation states (MnII → MnIV and TiIV → TiIII), which are able to activate multireactants and generate stabilized bromine radical (•Br) and hydroxyl radical (•OH) intermediates. As a result, the TiIV16MnII4 enables controlled tandem oxidation of C2H4/C3H6 to bromoethanol (BrCH2CH2OH)/bromopropanol (BrCH2CHOHCH3), ethylene oxide (EO)/propylene oxide (PO), and bromoacetic acid (BrCH2COOH)/bromoacetone (BrCH2COCH3) via shared (•Br + •OH)-dominated catalytic mechanisms, with high conversions (>99%), yields (up to 87%), and Faradaic efficiencies (FEs, up to 75%). Last but not least, this cascade catalytic system is applicable to a wide olefinic substrate scope as well as sustainable scaled-up production.

The practical application of lithium-sulfur (Li-S) batteries is severely hampered by the polysulfides shuttle effect and sluggish redox kinetics. Herein, a robust hydrogen-bonded organic framework material (HOF-PTPS) was developed via in situ incorporation of poly(3,4-ethylenedioxythiophene):poly (styrene sulfonate) (PEDOT:PSS) into a cyano-rich HOF for separator modification. The constructed multiple hydrogen-bonding network and the ordered hierarchical pore structure collaboratively established rapid Li+ transport channels while effectively inhibiting polysulfides migration. Systematic electrochemical analyses confirmed that HOF-PTPS significantly enhanced the sulfur reaction kinetics, as evidenced by higher Li+ diffusion coefficients, lower polarization, and reduced Tafel slopes. Ex situ and operando characterizations revealed their exceptional capability to anchor polysulfides via strong Li-N coordination, catalyze their conversion, and stabilize key S3 & centerdot; - radicals. Consequently, the polypropylene (PP) separator modified HOF-PTPS/ (PP) cell delivered a highly reversible capacity of 1172.8 mAh g-1 at 1 C, outstanding cycling stability, with 91.4% capacity retention of over 500 cycles, and stable operation under high sulfur loading. This work highlights the great potential of multifunctional HOFbased materials in developing high-performance Li-S batteries.