Nitrile-containing polymers feature extensively in consumer products and industry, yet efficient catalytic upcycling strategies remain underexplored. Herein, we report a general catalytic degradation strategy that enable...Nitrile-containing polymers feature extensively in consumer products and industry, yet efficient catalytic upcycling strategies remain underexplored. Herein, we report a general catalytic degradation strategy that enables the transformation of diverse nitrile-containing polymers via a tandem process combining nickel-catalyzed decyanation with ruthenium-catalyzed ethenolysis. This strategy enables cyano group removal and recycling into value-added nitrile compounds without releasing highly toxic cyanide species. Moreover, the process can be performed in a one-pot manner by employing ethylene as both the cyano group acceptor and the metathesis partner, thereby streamlining the degradation process, enhancing overall efficiency, and increasing potential for industrial adoption.
FeMn-based polyanionic phosphates, represented by NaFeMn(PO), are promising cathode materials for low-cost and sustainable sodium-ion batteries due to their high theoretical voltage and capacity. Nevertheless, their perf...FeMn-based polyanionic phosphates, represented by NaFeMn(PO), are promising cathode materials for low-cost and sustainable sodium-ion batteries due to their high theoretical voltage and capacity. Nevertheless, their performance is constrained by long-standing and unexplained anomalous electrochemical inertness. This study unveils the physical origin of this inertness and identifies an intrinsic electronic "spatiotemporal confinement effect". Spatially, PO tetrahedra separate the redox-active MO (M = Fe/Mn) units into mutually isolated compartments; temporally, spin-pairing constraints further impede charge transport within the d-electron configuration. Based on this mechanism, we propose a heterometallic bridging strategy by introducing V and Ti with empty 3d-orbitals as electronic bridges to reconstruct electronic connectivity within the Fe-Mn network. The prepared NaFeMnTiV(PO) successfully breaks the spatiotemporal confinement, circumvents spin-forbidden barriers, and activates multielectron redox reactions. Consequently, it achieves a leap from an inert state to high energy density of 470.1 Wh kg. Meanwhile, it exhibits exceptional wide-temperature adaptability, retaining 76.4 mAh g at -80 °C and operating stably across 130 °C range. This work elucidates the nature of electrochemical inertness in FeMn-based polyanionic compounds through the lens of spatiotemporal confinement and provides a universal strategy for the design of high energy density polyanionic cathode materials.
The air-water interface of aqueous microdroplets enables the spontaneous generation of hydroxyl radicals (·OH). However, the environmental fate and effect of these primary oxidants in complex, ion-rich media such as seaw...The air-water interface of aqueous microdroplets enables the spontaneous generation of hydroxyl radicals (·OH). However, the environmental fate and effect of these primary oxidants in complex, ion-rich media such as seawater remains uncharted. Here, we discover that the interface of seawater microdroplets sustains a radical cascade, which markedly amplifies their oxidative power beyond that of pure water microdroplets. Spontaneously produced ·OH at the interface quickly engages in synergistic reactions with abundant bromide and bicarbonate ions, initiating a network of secondary radicals, including reactive bromine (·Br) and carbonate (·CO) species. The coexistence and interconversion within this self-sustaining interfacial cycle are demonstrated through radical trapping and spectroscopic methods. To assess the environmental implications of this process, we have quantified its role in the dark oxidation of gaseous elemental mercury. Our findings advance the understanding from mere interfacial oxidant generation to the radical networks by specific ions, offering a novel framework for predicting chemical reactivity in environmental aqueous microdroplets.
Efficient NH capture remains a significant and unresolved challenge, despite its critical importance for resource utilization and sustainable development. To achieve this goal, adsorbents simultaneously featuring high ca...Efficient NH capture remains a significant and unresolved challenge, despite its critical importance for resource utilization and sustainable development. To achieve this goal, adsorbents simultaneously featuring high capacity, superior selectivity, and rapid adsorption kinetics are highly desired. In this work, we developed ionic liquid-loaded metal-organic framework (MOF/IL) composites by integrating highly NH-affinitive functional IL with anthracene-based MOFs featuring diffusion-facilitated channels. Benefiting from the ordering phase transitions of space-confined IL-NH, the composite presents a unique "S-shaped NH adsorption isotherm" and high volumetric NH uptake of 455.81 cm/cm at 298 K and 1 bar. Moreover, the additionally created pathways decorated with a high density of ionic sites localized within the original MOF enable the specific recognition of NH molecules while facilitating NH transport throughout the composite matrix, thereby ensuring both high selectivity and fast adsorption kinetics. Overall, this work offers a new paradigm and an easy method for designing functional soft porous materials for efficient gas capture.
Isotactic poly(propylene oxide) (PPO) is a semicrystalline polyether that has emerged as a high-strength, photodegradable material for marine applications. To improve the accessibility of PPO, catalysts with higher activ...Isotactic poly(propylene oxide) (PPO) is a semicrystalline polyether that has emerged as a high-strength, photodegradable material for marine applications. To improve the accessibility of PPO, catalysts with higher activity and selectivity are required. Using rational catalyst design informed by computational insights, we developed a flexibly tethered, bimetallic chromium catalyst exhibiting high enantioselectivity ( ∼ 100) and unprecedented activity (TOF ∼ 50,000 h) for propylene oxide (PO) polymerization. Mechanistic studies reveal that high enantioselectivity originates from increased steric bulk at the position of the salicylimine moiety, which increases steric repulsion between the alkoxide chain end and the ligand in the disfavored transition state. Furthermore, introducing geminal dimethyl groups that rigidify the flexible tether between the two ligand moieties significantly enhances catalyst activity by destabilizing the resting state during polymerization. The catalyst remains active at loadings as low as 0.5 ppm, enabling the synthesis of colorless, tough PPO.
In promising rechargeable magnesium batteries (RMBs), while empirical Cl addition to boron-based electrolytes optimizes Mg solvation structure and desolvation process, the scarcity of comparative halide anion studies has...In promising rechargeable magnesium batteries (RMBs), while empirical Cl addition to boron-based electrolytes optimizes Mg solvation structure and desolvation process, the scarcity of comparative halide anion studies has hindered the development of a systematic halide chemistry theory for electrolyte design. Br offers moderate solubility and mass efficiency comparable to Cl, superior to F and I, positioning it as an ideal platform to decouple the effects of halide identity on reaction kinetics, bridging a critical gap in fundamental mechanistic insights. Herein, leveraging the magnesium phenyl fluoroborate complex (MPFBC) electrolyte, we systematically synthesize MPFBC-Cl, MPFBC-Br, and the control electrolytes to elucidate how Cl and Br influence Mg plating/stripping kinetics from the bulk electrolyte to the interface. Specifically, the lower charge density and larger ionic radius of Br compared with Cl weaken Coulombic interactions with Mg, thereby facilitating ionic cluster dissociation and boosting bulk conductivity. The higher polarizability and chemical softness of Br relative to Cl drive stronger specific adsorption at the Mg interface, thereby reconstructing the inner Helmholtz plane and reducing the nucleation overpotential. Furthermore, Br promotes the formation of Mg-Br species in the SEI, which accelerates Mg transport across the interface. Benefiting from multiscale modification, the Mg|MPFBC-Br|Mg cell demonstrates improved Mg plating/stripping kinetics, evidenced by a low overpotential (<220 mV) and stable cycling for 1000 h at 1.0 mA cm, outperforming MPFBC-Cl and most conventional electrolyte systems. This study unveils the halide chemistry of Br in accelerating Mg plating/stripping kinetics, offering critical insights toward the rational electrolyte design for next-generation RMBs.
Electrocatalytic oxidation of alkenes represents a promising pathway for sustainable fine chemical synthesis in future chemical manufacturing. However, anodic propylene transformations typically yield only oxygenation pr...Electrocatalytic oxidation of alkenes represents a promising pathway for sustainable fine chemical synthesis in future chemical manufacturing. However, anodic propylene transformations typically yield only oxygenation products, such as propylene glycol, propylene oxide, acrolein, or acetone, lacking the important electro-driven C-C coupling process. Here, we report a C-C coupling pathway for propylene oxidation on Au, producing two C compounds: 2,5-hexanedione and 3-hexene-2,5-dione. Under mild conditions, the total Faradaic efficiency for C products reaches 36%. Combining in situ infrared spectroscopy, pressure-dependent experiments, and density functional theory calculations, it was revealed that the oxidative coupling proceeds through asymmetric coupling between *Pr and *PrOH intermediates, following the Langmuir-Hinshelwood mechanism. Simultaneously increasing the surface coverage of both C intermediates is crucial for efficient C-C coupling. These findings introduce an electro-oxidative C-C coupling strategy for propylene, providing new mechanistic insights into fine chemical electrosynthesis.
The disparity between the complex structures of synthesized materials and their simplified computational models leads to deviations between theoretically calculated and experimental performance. To narrow this gap, we in...The disparity between the complex structures of synthesized materials and their simplified computational models leads to deviations between theoretically calculated and experimental performance. To narrow this gap, we introduce the statistical descriptor φ, which is defined as the proportion of high-activity configurations in a given element combination. By considering the activity distribution of multiple structures rather than relying on a single model structure, φ can more accurately quantify macroscopic catalytic activity. Using the Seq-Equiformer model, a graph neural network we developed by augmenting EquiformerV2 with LSTM to capture dynamic structural changes during oxygen evolution reaction, we predict overpotentials for 250 million structures of 3d transition metal doped CoOOH. Based on these predictions, the value of φ for each element combination is calculated, and six optimal dopant combinations with the highest φ values are determined. For the leading MnFeNiCu combination, Bayesian optimization-driven AI experiments further optimize the elemental ratios. After only 40 experimental iterations, exploring 0.44% of the search space, the catalyst MnFeNiCuCoOOH is identified, delivering an overpotential of 246.5 mV at 100 mA cm and retaining 98.5% activity over 1000 h at 1 A cm. In validation, the statistical descriptor achieves 80% accuracy in identifying the top catalysts, a 30% improvement over single-structure screening, which evaluates the element combination based on the best configuration. The integration of statistical modeling, machine learning, and autonomous experimentation offers a powerful strategy to accelerate catalyst discovery and enhance prediction accuracy.
Enantioselective chlorination using sustainable chloride sources has long been a pursuit in organic synthesis. Moving away from stoichiometric, corrosive, and costly electrophilic reagents, we report the use of NaCl as a...Enantioselective chlorination using sustainable chloride sources has long been a pursuit in organic synthesis. Moving away from stoichiometric, corrosive, and costly electrophilic reagents, we report the use of NaCl as a green chlorine source for the enantioselective chlorination of organic molecules without the need for chemical oxidants. By leveraging electrochemical oxidation, we demonstrate the first electricity-driven enantioselective semipinacol rearrangement. Central to this approach is a dual-organocatalyst phase-transfer system that synergistically manages both phase transfer and enantiomeric induction. Notably, the implementation of alternating current (AC) proved essential in preventing catalyst deposition on the electrode surface, enabling high efficiency at a synthetically useful scale. This work represents a rare application of AC in asymmetric electrosynthesis and its inaugural use in organocatalysis. A variety of cyclic and functionalized ketones bearing all-carbon quaternary stereocenters were synthesized with high enantioselectivity and excellent functional group compatibility. Detailed mechanistic insights supported by control experiments and cyclic voltammetry as well as DFT calculation further elucidate the catalytic cycle. This protocol establishes a practical platform for future enantioselective chlorination processes using sustainable chloride sources.
The scaling relationship between the activity and selectivity of electrocatalytic hydrogenation reactions (EHRs) is caused by severe hydrogen evolution reactions and overhydrogenation because of the inevitable blocking o...The scaling relationship between the activity and selectivity of electrocatalytic hydrogenation reactions (EHRs) is caused by severe hydrogen evolution reactions and overhydrogenation because of the inevitable blocking of active sites through excessive adsorbed hydrogen (*H) at high current density. Herein, a spillover-storage-relaxation hydrogenation mechanism is proposed to overcome the scaling relationship. By employing acetylene (CH) to ethylene (CH) conversion as an example, Cu-supported atomically dispersed WO (WO/Cu), with abundant interfacial *H-formation Cu and *H-reservoir WO sites, is theoretically predicted and experimentally proven to be a promising catalyst. Consequently, WO/Cu is synthesized and demonstrates a CH partial current density of ∼1.43 A cm, with a CH Faradaic efficiency higher than 95%. The *H transfer from Cu to WO not only frees sites for CH adsorption but also reserves a hydrogen source for subsequent hydrogenation. Additionally, such a mechanism is suitable for Mo(W)O/Cu(Ag) in other EHRs.
Electronic correlations in two-dimensional (2D) systems are strongly governed by Van Hove singularities, which generate divergences in the density of states and enhance correlation effects. Although high-order Van Hove s...Electronic correlations in two-dimensional (2D) systems are strongly governed by Van Hove singularities, which generate divergences in the density of states and enhance correlation effects. Although high-order Van Hove singularities (HOVHSs) are typically associated with engineered band structures that require external tuning, their intrinsic emergence in realistic crystalline materials remains largely unexplored. We report on an interface-driven mechanism that intrinsically stabilizes a type-II HOVHS (emerged at nonregular points of the Brillouin zone) in an atomically thin Pb monolayer epitaxially grown on Si(111). Combining angle-resolved photoemission spectroscopy, scanning tunneling spectroscopy, and state-of-the-art calculations, we demonstrated that the HOVHS forms in close proximity to the Fermi level within Rashba-split surface states and produces a pronounced power-law divergence of the density of states exceeding that of conventional saddle points. We show that HOVHS arises without any external control and is stabilized by strong spin-orbit coupling and orbital hybridization at the Pb/Si interface. Our results establish an interface-driven mechanism for generating HOVHSs in spin-orbit coupled two-dimensional superconductors.
Iron (Fe) oxidation represents a prototypical system for understanding gas-solid reactions, directly impacting corrosion science, heterogeneous catalysis, and oxide-heterostructure design. Although the oxide configuratio...Iron (Fe) oxidation represents a prototypical system for understanding gas-solid reactions, directly impacting corrosion science, heterogeneous catalysis, and oxide-heterostructure design. Although the oxide configurations and oxidation pathways have been extensively documented, the atomic-scale structural dynamics that couple gas-surface reactions to solid-state phase transitions remain limited. Here, using in situ atomic-resolution environmental scanning transmission electron microscopy (ESTEM), we prepare atomically flat metal α-Fe(001) surfaces via thermal annealing and reveal a fundamentally different oxidation pathway from Fe to FeO during cooling under the ESTEM base vacuum. We demonstrate that metastable FeO plays a dynamically sustained role in two intermediate states. First, FeO nucleates on Fe(001) as distinct nanoscale islands below 300 °C, exhibiting a truncated square-pyramidal morphology. Second, FeO is retained as capping layers on the oxide during the transformation of the inner FeO into FeO, creating an inverted phase hierarchy (FeO/FeO/Fe). The FeO layers provide an active pathway for Fe diffusion, with their growth and transition dominating the subsequent oxide expansion. Despite the distinct growth behaviors of FeO on the (001) and {111} surfaces of oxide, their phase transitions are driven by a common basic unit. Structurally, the FeO-to-FeO transition is achieved via the translocation of octahedral Fe to tetrahedral sites, accompanied by outward diffusion. This work unveils the atomic-scale dynamics governing the coupled surface and interfacial reactions during the Fe oxidation via an island growth mode and establishes a new paradigm for understanding the unconventional oxide configurations in multilayer oxide-forming metals.
Precisely tailoring the macroscopic morphology of covalent organic frameworks (COFs) fundamentally drives their physicochemical properties. However, the robust and highly directional nature of covalent bonds makes such c...Precisely tailoring the macroscopic morphology of covalent organic frameworks (COFs) fundamentally drives their physicochemical properties. However, the robust and highly directional nature of covalent bonds makes such control at the single-crystal level a formidable challenge. Resolving this bottleneck, we establish a synergistic Brønsted and Lewis dual-acid catalytic strategy to dictate the controlled axial growth and morphological evolution of large (≥50 μm) three-dimensional(3D) COFs single crystals (the XNU-375-X; = 1-6, , , EtOH) featuring a topology. Modulating the concentration of dysprosium trifluoromethanesulfonate (Dy(OTf)), acting as the Lewis acid, drastically suppresses the twinning rate. Consequently, this targeted regulation drives a continuous morphological transition from octahedral to tetragonal bipyramidal geometries. Single-crystal X-ray diffraction (SCXRD) explicitly confirms the microscopic structural consistency throughout this macroscopic evolution. Crucially, during guest solvent removal and exchange, these crystallographic analyses directly capture a rare structural flexibility and dynamic "breathing" effect, evidenced by a massive 46% volume variation. Density functional theory (DFT) calculations elucidate the underlying growth kinetics. Conditional on the specific exposed facets ({100} versus {001}), Dy exhibits differential adsorption behaviors that effectively passivate lateral free amine sites. To the extent that these sites govern horizontal proliferation, this selective binding simultaneously promotes ordered -axis stacking and intrinsic self-correction. Ultimately, this work bridges the gap in the precision morphological tailoring of 3D COFs single crystals, providing a robust platform for the anisotropic growth and targeted synthesis of complex porous architectures.
The direct removal of carbonyl groups from cyclic ketones offers a nonintuitive but straightforward route to access multisubstituted saturated structural motifs via late-stage modification. However, such transformations...The direct removal of carbonyl groups from cyclic ketones offers a nonintuitive but straightforward route to access multisubstituted saturated structural motifs via late-stage modification. However, such transformations have been challenging to achieve, especially in a chemoselective manner. Here we report reductive and annulative carbonyl removal methods, enabled by the '-alkyl hydrazonamide (NAHA) reagents, via sequential double C-C bond cleavage. These transformations efficiently convert diverse cyclic ketones to the corresponding ring-opened and ring-contracted analogues with broad functional group tolerance. Besides late-stage modification of complex bioactive compounds, this carbonyl-removal strategy can also be applied to the synthesis of all-carbon quaternary centers lacking polar functional groups, terminal deuteration, and iterative ring contraction.
Bartoloni M, Balzo DD, Florencio-Zabaleta M
… +10 more, Mercogliano M, Bertuzzi S, Delgado S, Hernández I, Oiarbide M, Landa A, Diercks T, Unione L, Jiménez-Barbero J, Ardá A
Glycan-lectin interactions at cell surfaces regulate numerous biological processes but remain challenging to characterize at the molecular level. Glycosylation heterogeneity results in lectin-binding targets─from purifie...Glycan-lectin interactions at cell surfaces regulate numerous biological processes but remain challenging to characterize at the molecular level. Glycosylation heterogeneity results in lectin-binding targets─from purified glycoproteins to the cell-surface glycocalyx─presenting multiple glycan epitopes simultaneously. Concurrently, distinct lectins often exhibit overlapping glycan binding selectivity, with similar affinities for widely distributed epitopes. Consequently, how lectins compete and achieve selective recognition at glycoprotein and cell-surface levels remains poorly understood. Here, we introduce F lectin tagging, as an NMR-based approach to probe these complex glycan-mediated binding processes. Incorporation of F probes into lectins yields simple, background-free spectra, enabling binding studies in complex biological environments, including the cell surface. Importantly, this approach also allows the analysis of lectin mixtures with overlapping glycan specificities while individually resolving their binding behavior. We focus on galectins, a family of multifunctional and -acetyllactosamine (LacNAc)-binding lectins that regulate diverse processes at the cell surface, to dissect their competitive binding behavior across targets of increasing complexity, from small carbohydrates to glycoproteins and the cell-surface glycocalyx. Our results provide insight into the mechanisms underlying the recognition of the immune checkpoint glycoprotein TIM-3 by galectins and reveal competitive binding between some galectin family members at the cell surface. Collectively, these findings reveal that galectin specificity is not dictated solely by LacNAc recognition but instead arises from the molecular context in which glycans are presented, including multivalency and competition for shared glycan ligands. More broadly, they highlight the potential of F lectin tagging to investigate binding events in biologically relevant systems.
Photochemical upconversion by annihilation of two triplet excitons to a higher-energy singlet state enables energy control of photons in optoelectronics and photonics. Upconversion initiated by a closed-shell sensitizer...Photochemical upconversion by annihilation of two triplet excitons to a higher-energy singlet state enables energy control of photons in optoelectronics and photonics. Upconversion initiated by a closed-shell sensitizer is limited by energy losses from singlet-triplet intersystem crossing. Here we explore open-shell organic radicals as sensitizers and their closed-shell hydrogenated analogues as annihilators in photon upconversion. The sensitizer combines optical transitions from a triphenylmethyl (TTM-1Cz) radical with energy-degenerate triplet states of an anthracene-based component (DPA) in one molecule (TTM-1Cz-DPA). The difference of one hydrogen atom in its closed-shell counterpart (HTTM-1Cz-DPA) switches the spin-optical properties to an annihilator that can mediate efficient upconversion. Red-to-blue photon upconversion by intermolecular energy transfer, from open-shell sensitizer to closed-shell annihilator, is demonstrated in solution with an apparent anti-Stokes shift higher than 0.9 eV and 7% quantum efficiency. We evaluate this mechanism against true 'single component' mixtures for upconversion and find that the presence of hydrogenated precursor with radicals is essential for high performance. Understanding the emergent spin-optical properties from paired open-shell and closed-shell systems enables new opportunities for energy management from the same molecular frame.
Van der Waals layered transition metal thiophosphate CuInPS has attracted significant research interest due to its intriguing ferroelectric and optoelectronic properties. In this work, by combining high-pressure Raman sp...Van der Waals layered transition metal thiophosphate CuInPS has attracted significant research interest due to its intriguing ferroelectric and optoelectronic properties. In this work, by combining high-pressure Raman spectroscopy, optical absorption measurements, and ab initio calculations, we uncover a cascade of pressure-induced phase transitions in CuInPS. Remarkably, electrical transport measurements reveal the emergence of superconductivity above 58 GPa. The superconducting transition temperature increases progressively with pressure, reaching 15 K at 215 GPa─the highest reported to date among the metal phosphorus trichalcogenide (MPX) family. We attribute the origin of this high in CuInPS to a unique pairing mechanism characterized by dynamic carrier exchange between flat bands and highly dispersive bands dominated by sulfur vibrations. Our findings enrich the understanding of layered MPX materials and highlight pressure as a powerful tool for exploring high- superconductivity in sulfur-based systems.
We report the synthesis of three chloropnictogenium cations [MFluindECl] (, and ), which unravel different reaction pathways toward EtSiH, leading to the formation of the neutral arylarsenic(III) dihydride MFluindAsH ()...We report the synthesis of three chloropnictogenium cations [MFluindECl] (, and ), which unravel different reaction pathways toward EtSiH, leading to the formation of the neutral arylarsenic(III) dihydride MFluindAsH (), the cationic arylhydridostibenium(III) [MFluindSbH] () and the dicationic aryltribismuth(I) ion [MFluindBi] (). In light of its reactivity, can also be regarded as a protonated stibinidene(I), as demonstrated by the reaction with trimethylindium and gallium as well as diphenyldichalcogenides, leading to the stibinidene supported dimethylelement cations [MFluindSbEMe] (, ) and the chalcogenide cations [MFluindSbChPh] (, , ) featuring formal SbCh double bonds. The Bi dication reveals substantial 2-electron-3-center bonding character within the Bi-C-Bi interaction, a feature unprecedented in the chemistry of group 15 elements.
Catalytic, stereoselective carbon-carbon bond formation at nonanomeric positions of carbohydrates remains a long-standing challenge in organic synthesis. Here, we report a chiral-ligand-modulated, nickel-catalyzed stereo...Catalytic, stereoselective carbon-carbon bond formation at nonanomeric positions of carbohydrates remains a long-standing challenge in organic synthesis. Here, we report a chiral-ligand-modulated, nickel-catalyzed stereoselective radical migratory cross-coupling that achieves highly diastereoselective C2-arylation of carbohydrates directly from readily available 1-halosugars. A previously underexplored class of chiral 2-(aminomethyl)pyridine (Ampy) ligands is shown to impart catalyst-modulated stereocontrol in nickel-catalyzed cross-coupling. The reaction accommodates a broad range of aryl boronic acids and carbohydrate substrates, tolerates diverse functional groups and complex molecular architectures, and is amenable to gram-scale synthesis. Experimental and computational studies support a mechanism involving radical migration followed by a stereoselectivity-determining nickel-mediated radical capture governed by stabilizing ligand-substrate hydrogen-bonding interactions and destabilizing steric repulsion. This newly uncovered reactivity of chiral Ampy ligands provides a new strategy for stereocontrolled radical cross-coupling in polyoxygenated frameworks and expands the scope of stereoselective nickel catalysis.
Perovskite quantum dots (PQDs) are promising chiroptical materials owing to their soft ionic lattice and strong surface-lattice coupling. However, achieving efficient chirality induction in solid-state chiral PQD (CPQD)...Perovskite quantum dots (PQDs) are promising chiroptical materials owing to their soft ionic lattice and strong surface-lattice coupling. However, achieving efficient chirality induction in solid-state chiral PQD (CPQD) thin films remains a fundamental challenge. Here, we establish sterically constrained surface coordination as a strategy to promote chirality induction and lattice asymmetry in PQD solids. Using a synthesis-on-substrate approach, CsPbBr CPQD thin films with exclusive chiral ligand coverage are directly constructed, enabling well-defined ligand-surface interactions. Density functional theory calculations indicate that ligand coordination geometry, rather than ligand density, governs the strength of asymmetric interaction at the PQD surface. As a result, the CPQD films exhibit photoluminescence dissymmetry factors exceeding 10 across the tunable range of 468-515 nm, reaching 3.47 × 10 at 510 nm, and combine pronounced chirality-induced spin selectivity with high electrical conductivity. Spin light-emitting diodes based on the CPQD films achieve an electroluminescence dissymmetry factor of 0.15 and an external quantum efficiency of 17.9%. Our results highlight the role of coordination environment in chirality transfer and underscore the potential of CPQDs for spin-optoelectronic applications.