Developing materials with low thermal conductivity and a high power factor is crucial for the practical applications of thermoelectrics. The ZrBeSi-type structure has attracted significant research interest owing to its unique planar honeycomb lattice, which facilitates excellent electrical and thermal transport properties. In this work, we investigated the thermoelectric properties of ZrBeSi-type Zintl phase compounds BaLiX (X = P, As, Sb, Bi) using first-principles calculations based on density functional theory. Our results demonstrate that anion engineering decouples the thermal and electrical transport, leading to enhanced thermoelectric performance. Specifically, BaLiP exhibits the lowest lattice thermal conductivity (xL) of only 0.76 W m-1 K-1, which arises from its large phonon bandwidth that significantly enlarges the scattering phase space leading to stronger scattering effects that ultimately suppress xL. Moreover, the combination of a small direct band gap, multiple degenerate bands, and pronounced anisotropy electronic band structure in BaLiBi enables a high Seebeck coefficient and remarkable electrical conductivity. Consequently, enabled by anion engineering, n-type BaLiP achieves a ZT value of 1.01, attributed to its suppressed xL, while n-type BaLiBi reaches a ZT of 1.05 due to its outstanding power factor. Our work highlights anion engineering as a viable strategy for decoupling electronic and thermal transport, and elucidates the underlying physical mechanism governing the anomalous mass dependence of lattice thermal conductivity in ZrBeSi-type Zintl compounds.

Despite huge progress accomplished in perovskite light-emitting diodes (PeLEDs), the electroluminescence performance of blue PeLEDs lags far behind, constraining the widespread application of PeLED technology for vibrant full-colour displays1-5. The wider bandgaps of blue emitters require higher working voltages of corresponding electroluminescent devices, intensifying the octahedral instability of perovskites with ionic nature6,7. Here we report efficient and stable PeLEDs with saturated blue emissions by constructing hydrogen-bonding networks formed within perovskite and at the interface using isomeric molecules. The O-benzylhydroxylamine hydrochloride (OBCl) between the hole transport layer and the emitter acts as hydrogen-bonding donor, binding to the perovskite inorganic framework, which enhances the perovskite structural stability and decreases the hole energy barrier due to the large dipole moment. The isomeric N-benzylhydroxylamine hydrochloride (NBCl) added into the perovskite provides acceptor and donor sites for forming hydrogen bonding with the OB+ and the perovskite. The isomeric molecular hydrogen bonding reinforces the preferential orientation of perovskite films induced by OB+ interfacial molecules, improving the carrier mobility and further enhancing material stability. We demonstrate, as a result, blue PeLEDs with external quantum efficiencies of 16.8% at 463 nm and 22.0% at 468 nm, as well as significantly improved device stability, representing state-of-the-art performance among pure- and deep-blue PeLEDs.

Two-dimensional (2D) tin (Sn)-based perovskites are promising lead-free emitters for red light-emitting diodes (LEDs), but their intrinsically low carrier mobility and poor film morphology severely limit large-area performance. Here, we introduce a one-step antisolvent-assisted approach that disperses amino-functionalized multi-walled carbon nanotubes (CNTs) along the grain boundaries of phenethylammonium tin iodide (PEA2SnI4) films. The CNTs provide conductive pathways that accelerate carrier diffusion, while their ammonium groups regulate crystallization and improve film uniformity. Transient absorption microscopy and transport measurements confirm that carrier conduction is more than doubled in CNT-modified films. As a result, large-area (150 mm2) PEA2SnI4 LEDs achieve a maximum external quantum efficiency of 2.35% and a peak luminance of 5028 cd m-2, exceeding the threshold for outdoor-readable displays. This grain-boundary engineering strategy directly addresses the transport and morphology limitations of 2D Sn-based perovskites and establishes a scalable route to high-performance, lead-free optoelectronics.

Improving the photocatalytic performance via precisely tailoring molecular conformation remains elusive. Herein, we report a novel strategy for constructing conformation-restricted complexes by incorporating flexible chains. Using this approach, we synthesized three terpyridine-based charge-transfer (CT) complexes (S-12, S-13, and S-14) whose conformations were tuned by manipulating the flexible chain length. These conformation-restricted complexes were fully characterized and showed markedly different electronic structures and excited-state properties. Among them, S-12, with the shortest chains, adopts the most restricted conformation, which stabilizes the CT excited state and leads to the longest excited-state lifetime. From S-14 to S-12, the photocatalytic performance demonstrates a progressive enhancement, which can be attributed to enhanced exciton dissociation through stabilization of the CT excited state by more restricted conformations. This is a worthwhile example of improving photocatalytic performance through manipulation of restricted molecular conformation. Remarkably, complex S-12 achieves an outstanding H2O2 evolution rate of 7905 μmol g-1 h-1 in pure H2O under air, surpassing most reported organic photocatalytic systems.

ABSTRACT In biological systems, certain fundamental biomacromolecules, such as proteins and DNA, fulfill specific biological functions via structural changes triggered by stimuli. Herein, we report the synthesis of two allosteric regulation metal−organic octahedra ( S1 and S2 ) with tailored cavities/windows. Both cages exhibit distinct aggregation‐induced emission (AIE) colors and quantum yields. Single‐crystal x‐ray diffraction reveals that S2 , featuring longer arms, adopts a denser π‐stacking arrangement, rationalizing its superior emissive properties. The kinetically driven multicomponent heteroleptic octahedral mixtures formed under ambient temperature assembly conditions transformed into self‐sorted S1 and S2 upon heating. The addition of competitive building blocks enabled the transformation from S1 to S2 . Notably, 365 nm light irradiation induces planarization of the COT units, driving a rapid structural transformation from three‐dimensional (3D) octahedra to two‐dimensional (2D) metal–organic nanosheets ( NS‐1 and NS‐2 ) within minutes. This work provides a novel approach for designing responsive systems and demonstrates broad potential applications in areas such as optoelectronics, targeted delivery, and smart materials.

Tin halide perovskites are promising lead-free emitters for perovskite light-emitting diodes (PeLEDs), but their practical development is limited by fast crystallization, high defect densities, and the facile oxidation of Sn2+. Here, we introduce a synergistic dual-additive strategy based on urea and ammonium thiocyanate (NH4SCN) to simultaneously regulate crystallization and stabilize two-dimensional TEA2SnI4 films. Structural and spectroscopic analyses indicate that SCN- partially substitutes for surface I-, forming a TEA2SnI4/TEA2SnI4-xSCNx composite structure in which the stronger Sn & horbar;S interaction suppresses Sn2+ oxidation and enhances lattice stability. Meanwhile, urea improves film crystallinity and interacts with NH4 + through hydrogen bonding, promoting the release of coordination-active SCN- species and reinforcing surface protection. As a result, the dual-additive films exhibit lower trap densities, weaker nonradiative recombination, and markedly improved air stability. PeLEDs based on the optimized films deliver a peak external quantum efficiency (EQE) of 17.6% together with an operational T 50 exceeding 30 h at an initial luminance of 50 cd m-2. This work establishes a simple yet effective route toward efficient and stable lead-free Sn-based PeLEDs.

The intermediate-band solar cell (IBSC) entails the potential to achieve power conversion efficiency (PCE) beyond the Shockley-Queisser limit. To date, quantum dots (embedded in bulk perovskite matrices) are a main platform for making IBSC, but their efficiencies are still limited due to defects associated with heterogeneous components. Organic-inorganic halide perovskites (OIHPs), with numerous desirable material properties such as strong visible absorption, long carrier-diffusions length and high defect tolerance, can be an alternative promising candidate for realizing effective IBSC when intermediate-bands (IBs) are introduced. Herein, we show a theoretical design of extended OIHP-based IBSC by (1) enlarging the internal cage space in the OIHP through edge-sharing octahedra, and (2) by adding tunable aliphatic or aromatic diammonium (DAM) in the enlarged cage space. Moreover, the minor chemical modification of aromatic rings of the organic species allows tunable intermediate subbands and thus enables optimal subband structures for maximum absorption of sun light. This type of IBSCs not only will retain the novel properties of conventional OIHPs, but also will be free of the defects associated with the heterogeneous components, thereby offering a novel approach to achieve high PCE.

The structural principles of traditional Chinese mortise-and-tenon joints have inspired breakthroughs in supramolecular engineering. Nevertheless, substantial challenges remain in constructing nanoscale supramolecular architectures with precisely controlled giant dimensions. Herein, we report a precision-guided synthetic strategy for constructing giant 2D and 3D supramolecular architectures with rhomboidal motifs, which was achieved through a dovetail joint strategy. Initial assembly of bis-mortise ligand L1 with dovetail tenon ligand L2 in the presence of Cd2+ ions yielded the fundamental bis-rhombic supramolecule R1 . Subsequent structural elaboration of the dovetail tenon motif enabled the development of multitopic ligands L3 and L4 , which facilitated the construction of expanded architectures of the giant bis-propeller supramolecule R2 and tris-propeller supramolecule R3 . The synthesized supramolecules R1-R3 were fully characterized multidimensional NMR spectroscopy, electrospray ionization mass spectrometry (ESI-MS), traveling wave ion mobility mass spectrometry (TWIM-MS), transmission electron microscopy (TEM), and atomic force microscopy (AFM). This work develops an innovative dovetail-joint assembly strategy for constructing rigid giant supramolecular architectures, establishing a new paradigm for precision engineering of complex 3D molecular systems. (c) 2025 Published by Elsevier B.V. on behalf of Chinese Chemical Society and Institute of Materia Chinese of Medical Sciences.

Quantum dot light-emitting diodes (QLEDs) are promising candidates for next-generation lighting and display devices. However, the prevalent positive aging phenomenon currently plagues these systems. While positive aging can enhance device performance, its intrinsic uncontrollability induces device inconsistency, thereby posing a critical barrier to QLEDs commercialization. Herein, we propose a novel strategy involving the incorporation of Al2O3 nanosheets into ZnO, which effectively suppresses the positive aging phenomenon. The freshly fabricated devices deliver an external quantum efficiency (EQE) of 16.53 % and a current efficiency (CE) of 17.75 cd/A, comparable to those of reference devices after positive aging. Meanwhile, device stability is significantly improved: at an initial luminance of 1000 cd/m2, the T95 lifetime reaches 157 h, a 208 % enhancement relative to reference devices. Furthermore, the underlying mechanism for Al2O3 modification is elucidated in depth. Overall, this work introduces a novel and facile strategy for mitigating positive aging, thus paving a new avenue toward the fabrication of stable, high-performance QLEDs.

Architectured lamellar structures with flat interfaces in transition-metal carbide or nitride (TMC(N))/metal nano-multilayers have been extensively utilized for toughness enhancement, a perpetual pursuit in engineering applications. Recently, lithosphere-inspired architecture with a wavy pattern has provided a new avenue for further improving toughness via triggering a higher rate of mechanical energy dissipation than that of the flat lamellar pattern. Herein, the self-assembled TaC/TiNi lithosphere-inspired nano-multilayer architecture (wavy type) has been prepared by activating the Stranski-Krastanov (SK) growth mode and inducing solid-state dewetting during periodic layered deposition. The novel wavy TaC/TiNi lithosphere-inspired nano-multilayer demonstrates extraordinary fracture toughness, which can be attributed to the following mechanisms: (1) the wavy lamellar structure facilitates efficient stress transfer, thereby promoting uniform strain distribution and enabling extensive plastic co-deformation; (2) crack deflection along the wavy interlamellar interfaces between TaC and TiNi nanolayers extends crack propagation paths and increases energy dissipation. Our study reveals that the lithosphere-inspired nano-multilayer architecture can act as a design route for the construction of TMC(N)/metal nano-multilayers with exceptional damage tolerance

Protonic ceramic electrolysis cells (PCECs) have emerged as a promising solid-state ion device, attracting considerable attention for efficient hydrogen generation. However, PCECs face multiple constraints, most notably the lack of high-performance Co/Sr-free air electrodes. Because the current widely used air electrodes generally contain Co and Sr elements, they encounter serious problems of thermochemical expansion and Sr segregation. Traditional air electrode development primarily relies on experience-guided experiments and trial-and-error methods, which is time-consuming and inefficient in exploring vast material compositional spaces. The introduction of machine learning (ML)-driven discovery of air electrodes provides a transformative new approach to the fast development of PCECs. Here, based on the well-constructed ML models, high-performance novel Co/Sr-free Ca0.5La0.5Fe1-xScxO3-delta oxides are successfully designed as the air electrodes of PCECs. Among them, Ca0.5La0.5Fe0.8Sc0.2O3-s (CLFS0.2) oxide demonstrates exceptional properties, including the high hydrated proton defects amount (0.143 mol unit-1 at 550 degrees C), high catalytic activity, and low thermal expansion coefficient. As a result, PCEC with CLFS0.2 air electrode achieves a current density of 1.58 A cm-2 at 1.3 V at 650 degrees C, which is higher than the most of Co-free air electrodes and rivals mainstream Co/Sr-containing air electrodes.

Fe and Co doping induce ferromagnetism with T c > 300 K in triphenyl-amine graphdiyne while retaining its semiconducting properties. Devices assembled from such materials show a broadband and fast photoresponse.

The modulation of ferromagnetic order in 2D carbon materials has attracted increasing attention for the development of next-generation spintronic devices and multifunctional information storage technologies. In particular, the graphdiyne (GDY) family has been regarded as more suitable for spintronics owing to its tunable electronic structure and intrinsic semiconductor behavior. However, the effective magnetic introduction methods and their applications in specific devices have always been a challenge for the development of such materials. Here, this study presents a nitrogen-substituted derivative of GDY, triphenyl-substituted triazine graphdiyne (TPTG), as an ideal platform for inducing transition-metal iron (Fe) atoms to modulate the electronic state, resulting in the coexistence of room-temperature ferromagnetism and a semiconductor energy band. Subsequent spin-polarized density functional theory calculations further reveal that the observed ferromagnetism arises from pronounced localized magnetic moments together with electron transfer between carbon atoms and Fe ions. Moreover, by employing a transfer strategy suitable for this material system, thin films were successfully transferred onto a silicon substrate to construct an Fe-doped TPTG-based electronic device. Such a device exhibits typical artificial synaptic behavior under optical stimulation and demonstrates nonvolatile memory characteristics after illumination is removed, enabling the transition from short-term plasticity (STP) to long-term plasticity (LTP). The coexistence of ferromagnetism and semiconducting properties not only makes GDY-based materials promising candidates for exploring physical phenomena but also offers opportunities for the development of carbon-based neuromorphic devices.

Controllable modifications on dimensionalities and topologies of supramolecules are crucial for tuning their properties. Here, we report a robust component-controlled topological transformation, initiating with a two-dimensional (2D) layered coordination network S2 formed by the self-assembly of a metallo-organic ligand (MOL) LA with Zn(II). The strategic introduction of a V-shaped modulator LB with peripheral arms into the S2 system triggered a remarkable topological transformation, thus affording a discrete zero-dimensional (0D) hexagon-framed Star of David S1. This unprecedented 2D to 0D control facilitates direct comparison of their intrinsic properties, with structures unequivocally confirmed by nuclear magnetic resonance (NMR) spectroscopy, high-resolution electrospray ionization mass spectrometry (ESI-MS), traveling-wave ion mobility mass spectrometry (TWIM-MS), and microscopy. In the aerobic sulfide oxidation, the extended 2D network S2 exhibited significantly improved photocatalytic performance over S1. This enhanced efficiency was attributed to S2's pseudo-heterogeneous nature, which maximizes active site exposure and overcomes typical limitations of heterogeneous catalysts. This work not only establishes a novel strategy for controlling supramolecular architecture but also compellingly demonstrates that for catalytic applications, ensuring active site accessibility through judicious structural design can be a more potent strategy than pursuing isolated structural complexity.

Metallo-cages with distinctive cavities and intricate molecular frameworks have found extensive applications in diverse fields. However, it is still challenging to construct larger frameworks with high rigidity and complexity via facile methods and simple ligands, which is crucial for further applications of these alluring architectures. Herein, we propose a cage-on-cage assembly based on the development of a judiciously designed dendritic ligand that enables the bottom-up growth of a series of C2v-symmetric multitopic ligands (LA, LB, and LC). Through systematic increase of branches on the ligand, the assemblies were precisely controlled, yielding a series of supramolecular architectures with hierarchically increased complexity from a C2h-symmetric chairlike [Zn2LA2], to a C3v-symmetric bowl-shaped [Zn6LB3], and ultimately into a Td-symmetric giant tetrahedral cage [Zn36LC12]. Remarkably, the [Zn36LC12] metallo-cage achieved an unprecedented molecular weight of 51 kDa and an outer ball diameter of 6.7 nm, representing the largest single-component ligand-based molecular tetrahedron reported to date in terms of both molecular weight and physical dimensions. Owing to the high rigidity of the single-component framework, the [Zn36LC12] exhibited a superior fluorescence quantum yield of 60.3%. This research introduces an innovative hierarchical strategy for the architecture of single-component metallo-organic cages, which provides a promising candidate for the development of luminescent materials in advanced optoelectronics.

In this study, two metallo-organic triangular architectures (S1 and S2) based on iridium(III) complexes were successfully constructed. Electron paramagnetic resonance (EPR) analysis confirmed that S1 and S2 can efficiently generate reactive oxygen species (ROS) under light irradiation. In photocatalytic degradation experiments, both triangles exhibited outstanding performance toward rhodamine B (RhB). Specifically, S1 and S2 achieved degradation rates of 82.5% and 84.9% within 10 minutes, respectively. This work highlights the great potential of iridium-based supramolecular architectures in rapid and efficient photodegradation of organic pollutants.

The high directional alignment of continuous CNT fiber (CNTf) consisting of numerous carbon nanotubes (CNTs) makes it a potential reinforcement to construct novel CNTf reinforced Cu matrix (CNTf/Cu) composite. However, the interfacial properties between CNTf and Cu matrix can be severely deteriorated by contaminating O adsorbed on the surface of pristine CNTf. It is revealed that for CNTf/Cu composite, only similar to 16 nm-thickness Cu2O interfacial reaction layer (RL) is formed at CNTf/Cu interface; meanwhile, the excess contaminating O induces the amorphization of CNTs nearby CNTf/Cu interface, ultimately resulting in low tensile strength of similar to 301 MPa that is only similar to 69.8 % of the value calculated by rule of mixture (ROM). Notably, the introduction of highly oxygen-active Ti interlayer between Cu matrix and CNTf can sufficiently consume the surface contaminating O of CNTf to avoid the amorphization of CNTs and self-assemble in situ to form a similar to 170 nm-thickness TiO2 interface-modified layer, which enables its tensile strength to increase to similar to 417 MPa reaching similar to 91.9 % of the value calculated by ROM due to significantly improved interface strength. Moreover, self-assembling TiO2 interface-modified layer increases the thermal conductivity and electrical conductivity from similar to 350.8 W/m.K and similar to 5.08 x 10(7) S m(-1) in CNTf/Cu composite to similar to 377 W/m.K and similar to 5.39 x 10(7) S m(-1) in CNTf/Ti/Cu composite, respectively.

Although the structural framework for constructing regular polyhedral supramolecular cages from symmetric ligands is relatively well established, assembling distorted polyhedra using ligands of lower symmetry remains a considerable challenge. Herein, we report two distorted octahedral supramolecular cages, S1 and S2, based on a spirobiindane-derived rigid core with varying π-conjugation lengths and heteroatoms. The nearly perpendicular spirobiindane unit provides a rigid structural platform and promotes the formation of distorted cage-like structures. Octahedron S1 exhibited a high fluorescence quantum yield (ΦF) of up to 72.87% in pure DMF, and the ΦF increased to 96.24% in a DMF/H2O mixed solvent with 20% water content, surpassing that of most reported metal-organic cages. In contrast, the π-extended and heteroatom system S2 shows progressively red-shifted and aggregation-induced emission enhancement; however, the strong electron-withdrawing effect of the phenazine unit and the enlarged cavity size likely result in a significantly lower ΦF for S2 compared to S1. By reporting the synthesis of luminescent supramolecular cages with novel structures, this work further reveals how π-conjugation extension and heteroatoms modulate the emission behavior of supramolecular assemblies, thereby offering a new perspective for the rational design and construction of tunable luminescent supramolecular systems.

Carrier injection imbalance severely limits the performance of quantum dot light-emitting diodes (QLEDs), emphasizing the demand for advanced transport layer materials. Herein, a high-performance reduced graphene oxide (rGO) hole injection layer (HIL) is prepared by thermally treating graphene oxide (GO) at 160 °C for 30 min, which boosts current density by two orders of magnitude, and tunes work function to 5.04 eV, thus lowering hole injection barriers. rGO-based QLEDs exhibit excellent optoelectronic performance, featuring a 2.0 V turn-on voltage and a maximum luminance of 120 000 cd m-2. Their peak external quantum efficiency (EQE) and current efficiency are enhanced from 8.07% and 8.99 cd A-1 (for same-batch GO-based devices) to 11.51% and 12.65 cd A-1. Further optimization elevates their peak EQE and current efficiency (CE) to 13.31% and 14.93 cd A-1, respectively. Performance gains stem from enhanced rGO conductivity, with rGO-based devices boasting superior thermal stability and low-temperature operability. This study verifies thermally reduced rGO as an ideal high-performance HIL, offering a new possibility for QLED optimization.

The commercialization of perovskite solar cells (PSCs) is bottlenecked by inefficient trial-and-error approaches reliant on human expertise in both materials discovery and device fabrication1-3. Here we introduce an autonomous closed-loop framework that integrates machine learning (ML)-driven materials discovery with an automated manufacturing platform. The system uses active learning and quantum modelling to rapidly identify high-performance molecules and the platform uses Bayesian optimization and symbolic regression in a feedback loop to continuously refine the fabrication process. This integrated approach enabled the discovery of a passivation molecule, 5-(aminomethyl)nicotinonitrile hydroiodide (5ANI), which yielded 0.05-cm2 solar cells with a power conversion efficiency (PCE) of 27.22% (certified maximum power point tracking (MPPT) efficiency of 27.18%) and 21.4-cm2 mini-modules with a PCE of 23.49%. Moreover, the devices exhibited long-term operational stability, retaining 98.7% of their initial efficiency after 1,200 h of continuous operation under the ISOS-L-1I protocol. Crucially, the automated platform achieved an efficiency reproducibility nearly five times that of manual fabrication. This work establishes an automated closed-loop system that synergizes ML-powered discovery with the high-fidelity data from automated manufacturing, setting a benchmark for autonomous discovery and manufacturing in photovoltaics and materials.