Physics

Because of the temperature-induced intervalley scattering, transition metal dichalcogenides (TMDCs) typically exhibit diminished valley polarization at room temperature, limiting their application in valleytronic devices. To address this issue, combining chiral perovskites with monolayer TMDCs provides a promising route for room-temperature valley polarization control. Here, the enhanced chiral-induced spin selectivity (CISS) effect in R -(+)- and S -(−)-α-methylbenzylamine (MBA)–based tin perovskites is substantially strengthened by introducing chiral seed layers. Leveraging spin-valley coupling, spin extraction at the chiral perovskite interface improves the valley polarization of monolayer tungsten disulfide (WS 2 ) to reach as high as 14.9% at room temperature. The enhanced CISS effect enables more efficient spin-selective charge transfer, thereby amplifying the carrier population imbalance between the K and K′ valleys in monolayer WS 2 . This asymmetry is further improved by the high-quality chiral perovskite substrates, which help suppress valley carrier recombination. Our study offers a promising approach by combining chiral seed–induced enhancement of the CISS effect in chiral perovskite with monolayer TMDCs to achieve excellent performance of valley manipulation.

Covalent organic frameworks (COFs) unlock opportunities to unite rapid mass transport with molecular-level sieving through membranes. However, achieving long-range crystallographic order within these membranes remains a central challenge that limits their separation precision. Here, we report a monomer-driven strategy for the ambient-condition fabrication of COF polycrystalline membranes featuring definite lattice order and polyhedral textures, reminiscent of benchmark metal-organic framework counterparts. Using a rigid, π-conjugated pyrene-centered tetraamine, we enable nonepitaxial intergrowth of faceted COF crystals on a porous support, yielding a 350-nanometer-thick membrane with a record-high Brunauer-Emmett-Teller surface area of 2121 square meters per gram among COF separation membranes of comparable pore size. The resulting COF membrane preserves its crystallographic order and polyhedral texture even after 1 month of solvent exposure while uniquely combining increased surface stiffness with high tensile ductility. Notably, we demonstrate its superior liquid-phase molecular selectivity, outperforming COF analogs with considerably smaller pore apertures, and elucidate an unambiguous correlation between crystallographic order and permselectivity. This work positions crystallographic ordering as a guiding principle for COF membranes, opening more possibilities at the intersection of framework materials and separation technologies.

DNA nanotechnology leverages the molecular design resolution of the DNA double helix to fold and tile matter into designer architectures. Recent advances in bioinorganic chemistry have exploited DNA/Ag + affinity to carry out the templated reduction of silver nanoclusters. Here, we develop a unified method that leverages the topology of DNA triangles with embedded silver base pairs to nucleate controlled cluster growth in a mesoporous 3D lattice. Use of confocal fluorescence microscopy allows for the direct observation of reaction kinetics and reconstruction of the optical bandgap. These crystals yield molecular structures of Ag 4 and Ag 6 by x-ray diffraction in varying pyrimidine:pyrimidine pairs. Intercluster distances of less than 2 nanometers show observable electronic coupling, with red shifting observed relative to literature standards. A thorough computational investigation establishes a theoretical basis for our observed behavior and establishes the interplay between cluster size, charge, geometry, and resonance. We anticipate that these results will yield advances in materials synthesis, DNA-based plasmonic crystals, and optically active nanoelectronics.

Quantum logic gates based on quantum electrodynamics (QED) in strong coupling regime between quantum dots and microcavities are key elements for scalable quantum computing and all-optical quantum networks. Here, a single colloidal quantum dot was site-selectively positioned onto a dielectric photonic crystal hybrid microcavity using a soft nanoprobe technique, enabling the study of strong coupling between the colloidal quantum dots and bound states in the continuum in the cavity. By combining photoluminescence spectroscopy, Michelson interferometry, and continuous-wave pump-probe technology, the wavelength- and power-dependent phase shifts were systematically characterized. Controlled π-phase shifts of a single photon were experimentally demonstrated in both single colloidal quantum dot and high-concentration colloidal quantum dots coupled microcavity systems. This work provides an experimental basis for the development of room temperature quantum optoelectronic devices, including quantum phase gates and ultralow power optical switches.

Interfaces in oxide heterostructures act as critical regions to induce emergent and novel types of functionality in thin films. Herein, we demonstrate the creation of bulk ferroelectric heterostructures (BFHs) in monolithic ferroelectrics by nanoscale elemental partitioning, unlocking functionalities beyond the reach of conventional ferroelectrics and thin-film devices. The unique percolating, compositionally modulated networks act as built-in heterointerfaces that generate coupled ferroelectric-electrostatic-elastic fields, which stabilize charged domain walls and imprint predefined domain configurations throughout the bulk. In exemplar BiFeO 3 -BaTiO 3 ceramics, the BFH approach raises the Curie temperature to 824°C (increment Δ T C > 350°C) and yields superior high-temperature piezoelectric responses ( d 33 > 400 picocoulombs per newton, k 33 > 0.4), surpassing those of existing high-temperature piezoelectrics. Domain-engineered BFHs further unlock programmable control of domain switching, enabling the strongest yet tunable internal bias fields (>8 megavolts per meter) in bulk materials and record-high reversible shear electrostrains (up to 0.98%) at supercoercive field levels. The BFH design concept provides a transformative platform for next-generation ferroelectric and electromechanical transduction devices with extended temperature, high-power, and high-stress capability. It also establishes a universal framework for programmable control across ferroic families, including ferroelastic, ferromagnetic, and multiferroic materials in polycrystalline, single-crystal, and thin-film forms.

Angular-momentum transport provides a pathway for controlling energy flow in solids beyond conventional charge-based mechanisms. Although spin currents are known to mediate spin-caloritronic phenomena such as the spin Peltier effect (SPE), the role of orbital angular momentum (OAM) in heat transport remains largely unexplored. Here, we demonstrate OAM-driven temperature modulation via the SPE in yttrium-iron-garnet/Pt/CuO x heterostructures. Using wedge-shaped CuO x layers combined with spatially resolved active thermal measurement techniques, we map the continuous thickness dependence and quantitatively disentangle the spin- and orbital-current-mediated contributions within a single device. The orbital-mediated component exhibits a pronounced maximum at an intermediate thickness, revealing a characteristic length scale for interfacial OAM generation and propagation at the Cu/CuO x interface. These results provide direct experimental evidence that charge-current-driven OAM can drive SPE-induced temperature modulation, establishing interfacial orbital processes as an additional channel for heat transport and providing a pathway toward spin-orbit caloritronics.

Quantum many-body devices suffer from imperfections that destabilize dynamics and limit scalability. We show that the dynamical growth of entanglement can intrinsically protect generic quantum dynamics against coherent noise and local perturbative noise. Through rigorous theoretical analysis of general quantum dynamics and numerical simulations of spin chains and fermionic lattices, we prove that entanglement entropy growth confines the influence of local Hamiltonian perturbations, thereby suppressing dynamical errors. The degree of protection correlates quantitatively with the entanglement entropy of subsystems, on which the perturbations act, and applies broadly to both analog quantum simulators and real-time control protocols. This entanglement-induced resilience is conceptually distinct from quantum error correction or dynamical decoupling: It passively leverages native many-body correlations without additional qubits, measurements, or control overhead. Our results reveal a generic mechanism linking entanglement growth to dynamical stability and provide practical guidelines for designing noise-resilient quantum devices.

Abstract Sulfide-based lithium-ion solid electrolytes are promising candidates for solid-state batteries due to their high ionic conductivities, although they typically exhibit high moisture sensitivity. Li4SnS4 has recently attracted scientific interest because it exhibits higher moisture resistance than most other sulfide electrolytes. Two orthorhombic Li4SnS4 polymorphs (α and β) are known, yet their temperature-dependent phase behavior remains unexplored. Differential scanning calorimetry and temperature-dependent powder X-ray diffraction revealed that α-Li4SnS4 transitions to β-Li4SnS4 at 96 °C. Furthermore, we identified a second, previously unknown reversible phase transition from β-Li4SnS4 to a new γ-polymorph at 196 °C. Other phase transitions from −150°C to 1000°C were not identified. All polymorphs crystallize in space group Pnma (no. 62) and feature identical zig-zag-like arrangements of SnS44– tetrahedra. The main structural differences lie in the ordering of the lithium substructure. By combining temperature-dependent powder X-ray and neutron diffraction with high-temperature 7Li and 119Sn NMR as well as Raman spectroscopy, we show that Li4SnS4 transitions from the lithium-vacancy-disordered α-phase to the ordered β-phase and finally to the disordered γ-Li4SnS4. Using electrochemical impedance spectroscopy, we measured ionic conductivities from 10–6 S cm–1 to 10–1 S cm–1 between 25 °C to 220 °C. Conductivity changes are gradual, consistent with the subtle structural variations among all polymorphs.

Abstract Many of the materials under consideration as battery electrodes are known to exhibit polarons─charge carriers localized through polarizing their environments, which are unfortunately quite costly to tackle by theory. Next to costly ab initio methods and geometry optimizations, the main problem is the sheer number of possible configurations polarons can adopt in a material. This problem is exacerbated by symmetry-breaking defects such as oxygen vacancies ubiquitous in oxide materials. Fortunately, a majority of polaron configurations tend to be too high in energy to ever be adopted at normal operating temperatures. In this work, we therefore present a data-driven approach based on gradient-boosted decision trees as a descriptor for relative polaron energies. We demonstrate the efficacy of this approach to weed out those configurations that are energetically unlikely in three simulation cells of defected spinel Lithium4Titanium5Oxygen12 (LTO). The first two cells differ by their 16d-site occupational disorder and the position of the oxygen vacancy, which in both cases leads to the formation of two polarons in the cells. In contrast, the third simulation cell contains an extra lithium ion, which leads to three polarons. Our approach allows us to reduce the number of necessary first-principles calculations by roughly two-thirds. It can easily be adapted to other materials and simulation cells, greatly speeding up their theoretical treatment.

Abstract Oxygen loss in magnetite drives the cation redistribution and local structural reconstruction that control the rate of iron oxide reduction, but this coupling has resisted direct simulation: the reconstruction develops far beyond DFT-accessible scales, and classical potentials cannot describe mixed-valence Fe–O with the required fidelity. We developed a DFT-validated Fe–O Deep Potential trained on bulk, defective, and surface configurations and applied it in large-scale molecular dynamics with an imposed stochastic oxygen-removal protocol. The potential reproduces DFT energy and force trends together with vacancy and surface energetics. DFT single-point checks on oxygen-deficient configurations and equation-of-state calculations for Fe3O4 and FeO further delineate the transferability of the potential, with larger deviations emerging in the most strongly oxygen-deficient states. As oxygen is removed, four-coordinated O environments decrease while six-coordinated wüstite-like motifs emerge, grow, and coalesce into extended local domains. Deep-Potential nudged elastic band (DP-NEB) calculations, benchmarked against selected DFT single-point energies, show that the coupled O/Fe-vacancy configuration gives the lowest Fe-migration barrier among the selected local rearrangement pathways. Time-windowed mean-squared displacements yield apparent Fe and O diffusivities that evolve in the nonstationary lattice. These simulations establish a defect-mediated solid-state response toward wüstite-like local order under imposed oxygen-deficient conditions, rather than the formation of a complete equilibrium Fe1–xO phase. The protocol isolates oxide-side reconstruction and does not explicitly treat hydrogen chemistry.

Abstract Multi-electron-proton coupling reactions are fundamental in renewable energy conversion and environmental cleanup. However, achieving high catalytic efficiency and product selectivity remains a formidable challenge, primarily due to the complex transformations of intermediates, sluggish reaction kinetics, and intense competition from side reactions. In recent years, spin regulation has emerged as a crucial strategy to address these issues. By engineering spin states and controlling spin polarization, the electronic structure of catalysts can be effectively reconfigured, thereby optimizing the adsorption and desorption of intermediates and regulating charge transport and reaction pathways. This review comprehensively summarizes recent progress in spin-regulation strategies for key multi-electron reactions, including CO2RR, NRR/NO3RR, ORR, and water-splitting catalysis involving OER and HER, and further examines the roles of structural identity and reaction-dependent spin-electronic configurations in governing active-site function. We emphasize that different local spin configurations can each enhance catalytic performance under appropriate reaction conditions, whereas no single spin state can be regarded as universally superior. Accordingly, identification of the operative active site requires consideration of both its structural identity and its reaction-dependent spin-electronic state under working conditions. Within this framework, special attention is given to the roles of doping, defect engineering, coordination modulation, external fields, and multimetallic cooperation in regulating active-site identity, intermediate energetics, charge transfer, and product selectivity. Finally, we discuss current challenges and future directions for identifying operative active sites and establishing predictive design principles for efficient multi-electron catalysis. Overall, this review provides mechanistic insights and practical guidance for identifying operative spin-regulated active sites and rationally designing efficient and selective catalysts for multi-electron reactions.

Abstract Plasmon-induced hot-carriers generated through Landau damping underpin applications in plasmonic optoelectronics, energy conversion, and photocatalysis. However, it remains unclear whether these carriers retain the spatial localization of their parent plasmon modes or rapidly lose this spatial memory through ultrafast scattering and transport. Here, we experimentally probe the spatial and temporal dynamics of plasmon-induced hot-carriers in a strongly confined plasmonic structural color consisting of disordered aluminum nanoparticle ensembles on near-field cavities. Strong interparticle coupling produces hybridized and localized gap plasmon modes with intense nanoscale electromagnetic confinement, which we directly visualize using scattering-type scanning near-field optical microscopy. Ultrafast pump–probe measurements selectively excite a homogeneously broadened sub-ensemble of plasmonic modes, enabling indirect tracking of pump-generated, plasmon-induced hot-carrier dynamics. We observe that hot-carriers undergo only partial spatial delocalization and retain signatures of the initial plasmonic localization for hundreds of picoseconds. The perturbed sub-ensemble reaches maximum line widths of 0.54 ± 0.06 eV (0.36 ± 0.05 eV) under 630 nm (700 nm) excitation. On a phenomenological localization scale from 0 (localized) to 1 (fully delocalized), this corresponds to 0.35 ± 0.10 and 0.09 ± 0.08 for 630 and 700 nm excitation, respectively. The wavelength-dependent fraction shows that the degree of preserved localization is optically tunable, set by the carrier energy. This persistence of spatial memory, likely arising from disorder-induced scattering within the nanoparticle ensemble, reveals an unexpected spatial dimension of hot-carrier dynamics and highlights the role of plasmonic confinement and structural disorder in governing nanoscale energy flow, with implications for hot-carrier-based optoelectronics.

Abstract Perovskite light-emitting diodes (LEDs) have attracted significant attention owing to their rapidly increasing external quantum efficiencies (EQEs). However, achieving bright and operationally stable perovskite LEDs remains a great challenge. Here, we reveal that the most commonly used surface modifier of zinc-oxide (ZnO) electron-transport layer, polyethylenimine ethoxylate (PEIE), inhibits the perovskite nucleation by inducing in situ chemical reactions of perovskite precursor components, forming thermally unstable interfacial species and reducing long-term operational stability of resultant devices. We develop a surface-engineering strategy by using an ether-based polymer modifier to regulate perovskite crystallization kinetics and simultaneously suppress ZnO-induced deprotonation during long-term device operation. As a result, the optimized near-infrared (NIR) perovskite LEDs exhibit a maximum EQE of 24% and a peak radiance of 539 W sr–1 m–2, along with significantly enhanced operational stability. Furthermore, partial substitution of FA with Cs confirms the generality of this strategy, yielding bright NIR devices with an operational half-lifetime of 561 h at 20 mA cm–2.

Lithium-Sulfur Batteries This cover illustrates a slimmed solvation structure regulation strategy for lithium-sulfur battery electrolytes. Under lean electrolyte and high polysulfide concentration conditions, Li+ is heavily “bound” by anion aggregates (Sn2− and TFSI−); by introducing symmetric cations, the excess anions around Li+ are precisely stripped away, ensuring rapid Li+ transport under lean electrolyte conditions. Meanwhile, the symmetric cations assemble into a uniform positively charged layer at the anode interface, inducing the formation of a dense and stable SEI film. This strategy breaks through the core bottlenecks of energy density, safety, and cycle life, providing a new direction for the design of high performance, high-safety lithium-sulfur batteries. More details can be found in the Research Article by Fangyuan Hu and co-workers (DOI: 10.1002/adma.74357).

3D Moiré Architectures in Complex Oxides In their Research Article (DOI: 10.1002/adma.74365), Young-Hoon Kim, Miaofang Chi, and co-workers establish atomically coherent, chemically bonded interfaces in twisted oxide membranes using a controlled oxygen-annealing approach. This advance overcomes a major bottleneck in oxide twistronics by enabling interfacial coupling in membranes containing volatile elements, opening a pathway to strain-tunable oxide moiré heterostructures with emergent ferroic and quantum phenomena for next-generation electronic systems.

Protective materials for harsh environments should dissipate transient impact energy while maintaining mechanical reliability under thermal fluctuations. Here, we report a bioinspired twisted brick-mortar composite that integrates a carbon-nanotube-reinforced photopolymer framework with a mechanically active shear-stiffening gel mortar. The continuously twisted brick architecture redistributes stress waves and guides crack deflection, whereas reversible interfacial hydrogen bonding and dynamic boron-oxygen crosslinking enable rate-dependent molecular dissipation. This structural-molecular coupling provides efficient impact protection, delivering a low energy transfer rate of 7.38% under high-strain-rate compression and reducing the residual impact force from 20°C to 100°C. The carbon-nanotube-containing framework further provides photothermal responsiveness, allowing reversible stifhefness modulation, adaptive force buffering, and shape recovery after localized high-speed impacts. Together, these results establish a bioinspired twisted brick-mortar design strategy for adaptive thermo-mechanical impact protection.

ABSTRACT Layer‐structured transition metal oxides show great potential in alkali metal ion batteries, their structural phase transitions, however, lead to mechanical disintegration, resulting in capacity decay and severely limiting the lifespan. Traditional modification strategies struggle to suppress phase transitions at their thermodynamic root cause, while the ideal solid‐solution reaction paradigm faces the challenge of difficult‐to‐control electronic structures. A novel physical paradigm was proposed that drives the solid‐solution‐dominated reaction by reshaping the electronic state through a quenching process herein. A locally disordered layered oxide, K 0.5 (Mn 0.85 Fe 0.1 Ti 0.05 ) 0.99 (V TM B i ) 0.01 O 2 (KMFTB), was constructed through a quenching‐assisted vacancy‐mediated boron (B) incorporation process, in which TM vacancies (V TM ) capture B i and reconstruct the local coordination into stable [BO 4 ] units. Experiments and theoretical calculations confirm that the synergistic interaction between the locally disordered structure and strong B─O bonds not only stabilizes the transition metal framework through the pinning effect, but also induces a significant band broadening and electronic delocalization. This electronic structure restructuring enables KMFTB to suppress destructive phase transitions and achieve a highly reversible solid‐solution‐dominated reaction pathway, providing profound theoretical insights for the rational design of high‐performance cathode materials.

ABSTRACT Nucleic acid‐based gene therapeutics hold great potential for precisely treating pancreatic ductal adenocarcinoma (PDAC), yet their clinical translation remains challenged by the lack of efficient delivery platforms capable of simultaneously minimizing payload leakage, intrinsic toxicity, and immunogenicity. Herein, we report an acid‐activatable nucleic acid nano‐prodrug based on rolling circle replication, which directly integrates a large number of amplified Cas12/crRNA ribonucleoproteins (RNPs) and antisense oligonucleotides (ASOs) with minimal excipients, achieving tumor‐specific activation for PDAC combined gene therapy. The nano‐prodrug is assembled from a polymeric crRNA chain conjugated with Cas12a (Pro‐RNPs) and a polymeric ASOs chain (Pro‐ASOs)—the latter incorporating AS1411 aptamers for cancer targeting and HhaI cleavage sites for stimuli‐responsive release—while being surface‐loaded with acid‐degradable polymer‐coated HhaI enzymes. Upon PDAC uptake, the nano‐prodrug is activated within acidic lysosomes through degradation of HhaI enzymes’ polymer coating. HhaI cleaves specific recognition sites while overexpressed ribonuclease H hydrolyzes the RNA strand in DNA‐RNA heteroduplexes. These combined cleavage events disrupt the nano‐prodrug, enabling efficient co‐release of ASOs and Cas12a/crRNA RNPs for precise gene silencing and editing. In vivo studies in PDAC‐bearing mice demonstrate potent antitumor activity with minimal systemic toxicity or immunogenicity, presenting a promising strategy for precision gene therapy in pancreatic cancer.

Surface SOx Species Stabilized PtNi Featuring a PtNi nanoalloy, this artwork highlights the critical role of surface SOx species in anchoring metal-oxygen bonds, which boosts kinetics for seawater hydrogen production and provides a robust defense against chloride adsorption. More details can be found in the Research Article by Xiao-Yu Yang, Yu-Xuan Xiao, and co-workers (DOI: 10.1002/adma.73843).

ABSTRACT Fluorescence‐guided surgery is challenged by nonspecific fluorescence signaling of the conventional probes, leading to incomplete tumor resection. Moreover, chemotherapy‐mediated adjuvant therapy is frequently compromised by systemic toxicity and drug resistance. In this study, we developed a sequential theranostic chimera (namely SEQTAC) for sequentially activating intraoperative tumor margin diagnosis and postoperative residual tumor clearance. The SEQTAC was rationally designed by covalently integrating an enzyme‐labile hemicyanine derivative (namely HCy‐Br) with a thioketal bond‐modified proteolysis‐targeting chimera (PROTAC) of BRD4. Upon spray administration, the SEQTAC can be internalized by tumor cells and specifically activated by cathepsin B in the lysosomes. The HCy‐Br fluorophore was rapidly lighted up for intraoperative diagnosis of tumor burden and fluorescence imaging‐guided tumor resection. After postoperative spraying, the HCy‐Br fluorophore generated singlet oxygen upon 655 nm laser irradiation to perform photodynamic therapy and restore the PROTAC for BRD4 degradation in tumor cells, and thus enabled postoperative dissection of the unresectable tumor residue. The SEQTAC significantly inhibited the tumor relapse and elongated animal survival in mouse models of breast and glioblastoma tumors, which provided a promising platform for precise tumor surgery and postoperative tumor management.

ABSTRACT Control of spin‐current absorption in non‐magnetic materials is central to realizing spin‐current switches and low‐power spintronic technologies, yet anisotropic responses have so far been limited to a narrow class of crystalline materials. Here we demonstrate giant chirality‐induced anisotropic spin‐current absorption (CASA) in solution‐processed chiral hybrid organic–inorganic semiconductors (HOISs), establishing them as a versatile platform for symmetry‐selective spin manipulation. Zero‐dimensional [ R/S/rac ‐MBA] 4 Bi 2 Cl 10 (MBA = α ‐methylbenzylammonium) HOISs exhibit more than an order‐of‐magnitude variation in spin absorption between orthogonal spin polarizations. Strikingly, despite the lack of chiroptical activity, racemic films exhibit a similarly strong spin anisotropy, indicating that global crystallographic chirality is not a prerequisite for CASA. Structural chirality analysis reveals that the CASA is governed by the orientation of local chiral axes associated with the organic cations in HOISs. These results establish molecular chirality as an active design parameter for manipulating spin transport, positioning HOISs as a broadly compelling platform for spin‐based functionalities.

ABSTRACT Direct recycling of spent lithium‐ion battery (LIB) cathodes holds great promise for sustainable materials recovery. However, residual fluorinated impurities, including inorganic fluoride species and polyvinylidene fluoride (PVDF), remain a persistent challenge due to their chemical persistence and heterogeneous distribution. Here, we report an electrochemically driven self‐cleaning strategy that enables fluoride‐free adaptive direct recycling of spent cathodes. Using LiNi 0.5 Co 0.2 Mn 0.3 O 2 (NMC532) as a model system, anodic polarization activates oxygen‐evolution‐driven surface reconstruction, generating hydroxylated transition metal (TM) interfaces that trigger the cooperative elimination of fluorinated contaminants. Specifically, the reconstruction promotes proton‐assisted dissolution of LiF and related inorganic fluoride species, while simultaneously inducing a hydrophobic‐to‐hydrophilic interfacial transition that weakens PVDF adhesion and facilitates its removal. These coupled redox‐hydrolysis‐interfacial processes synergistically eradicate fluorinated residues while preserving the bulk composition and structural integrity of the cathode. The regenerated NMC532 delivers a high discharge capacity of 145.1 mAh·g −1 , comparable to commercial material. When implemented in pouch cells, this strategy achieves an inter‑batch capacity variation of less than 1.3%, dramatically outperforming the ∼24.1% variation typical of conventional recycling and meeting commercial consistency standards (± 3%–5%). This reconstruction‐enabled self‐cleaning strategy is broadly applicable across diverse cathode chemistries, providing a scalable and chemically selective pathway toward impurity‑free, high‑performance battery material regeneration.

ABSTRACT Controlling the spatial organization of ions in polymeric photocatalysts remains a fundamental challenge for optimizing charge transport and catalytic selectivity in solar‐driven hydrogen peroxide (H 2 O 2 ) synthesis. In conventional poly(heptazine imide) (PHI), alkali cations are incorporated through molten‐salt‐mediated equilibration, producing statistically distributed ionic environments with little spatial correlation. Here, we demonstrate that organic‐inorganic ionic cocrystals (ICCs) serve as molecularly preorganized precursors that promote spatially correlated ionic environments during framework formation, enabling controlled incorporation of Li + into imide‐bridged N sites. This ICC‐programmed architecture decouples composition from photocatalytic function, demonstrating that photocatalytic activity is governed by the ion incorporation pathway and the resulting spatial ionic organization, rather than cation identity or content alone. The resulting ionic carbon nitride, CALiK, achieves an apparent quantum yield of 58% at 410 nm, the highest among the benchmarked state‐of‐the‐art photocatalysts, while requiring substantially lower inorganic salt loading than conventional ionothermal synthesis. Operando‐relevant spectroscopic and electrochemical analyses reveal directional charge migration driven by internal electrostatic polarization and enhanced accumulation of long‐lived photogenerated electrons. Representative density functional theory models suggest that spatially correlated ionic motifs and cyano‐derived electron‐accepting domains generate polarized charge landscapes that lower the energetic barrier for the two‐electron oxygen reduction pathway.

Electrochemical Biosensors This cover image illustrates the implantation of a wireless bioelectronic implant with transient geometry into the subcutaneous space. Minimally invasive foldable bioelectronic implant (MiFi) miniaturizes up to six-fold for syringe insertion and autonomously unfolds post-implantation to achieve multiplexed and multimodal monitoring of cardiac and respiratory activity, subcutaneous temperature, tissue pH, and lithium dynamics. More details can be found in the Research Article by Selin Olenik, Firat Guder, and co-workers (DOI: 10.1002/adma.73923). Cover image illustrated by Muhammed Mehdi Menteş.