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Concurrent superconductivity and negative photoconductivity (NPC) are rarely observed. Here, the discovery in PbSe 0.5 Te 0.5 of superconductivity and photoconductivity transitions between positive photoconductivity (PPC) and NPC during compression is reported to ≈40 GPa and subsequent decompression, which are also accompanied by reversible structure transitions (3D Fm 3 ¯ ${{\bar{3}}}$ m ⇌ 2D Pnma ⇌ 3D Pm 3 ¯ ${{\bar{3}}}$ m). Superconductivity with a maximum T c of ≈6.7 K coincides with NPC and structure transition of Pnma to Pm 3 ¯ ${{\bar{3}}}$ m at ≈18 GPa and the latter phase is preserved down to ≈5 GPa with enhanced T c of ≈6.9 K during decompression. The observations imply the simultaneous superconducting and photoconductive transitions are closely related to the metallic Pm 3 ¯ ${{\bar{3}}}$ m phase. First-principles calculations suggest the enhanced p-p hybridization and charge transfer between Pb-5p and ligand-p orbitals near the Fermi surface play key roles in electron-phonon interaction of mediating the Cooper pairs in PbSe 0.5 Te 0.5 . Hall coefficient measurements reveal that photothermal effect enhances electron-phonon interplay, which decreases carrier concentration and mobility and results in the reversal of PPC-NPC. Structure-dependent superconductivity and NPC are jointly mediated by electron-phonon interplay, which is tunable through illumination or cooling at high-pressure. The findings shed light on the origin of superconductive and photoconductive transitions in versatile materials of lead chalcogenides., (© 2024 Wiley‐VCH GmbH.)

The intrinsic compromise between strength and toughness in composite epoxy resins significantly constrains their practical applications. In this study, a novel strategy is introduced, leveraging interfacial π-π stacking interactions to induce the "rolling behavior" of microsphere fillers, thereby facilitating efficient energy dissipation. This approach is corroborated through theoretical simulations and experimental validation. The resulting composite epoxy resin demonstrates an impressive 49.8% enhancement in strength and a remarkable 358.9% improvement in toughness compared to conventional epoxy resins, accompanied by substantially reduced hysteresis. Moreover, this system achieves reversible closed-loop recyclability and rapid repair capabilities. The preliminary demonstration of "force-temperature equivalence" further establishes a novel pathway for the design of high-performance composite epoxy materials., (© 2024 Wiley‐VCH GmbH.)

Carbon dots (CDs) have gained significant interest because of their potential in biomedical applications. Nevertheless, developing CDs with efficient photoinduced charge separation for tumor photodynamic therapy (PDT) remains a challenge. This study presents a novel class of supra-carbon-dots (supra-CDs) developed by fusing red emissive CDs with 2,3-dicyanohydroquinone (DCHQ) via post-solvothermal treatment. In supra-CDs, the core, acting as electron donors, is formed by assembled CDs with substantial sp 2 domains, the fused interface originating from DCHQ with electron-withdrawing groups functions as the electron acceptor. This configuration creates the unique donor-acceptor nanostructure. Upon white light irradiation, the excited electrons from the assembled CDs were transferred to the electron-withdrawing interface, whereas the photogenerated holes were retained within the assembled CDs as radicals, leading to effective photoinduced charge separation. The separated photogenerated electrons then react with oxygen to generate superoxide radicals. Simultaneously, the photogenerated holes undergo oxidation of crucial cellular substrates. This dual action underscores the exceptional cell-killing efficacy of supra-CDs. Moreover, the increased particle sizes (~20 nm) ensure supra-CDs to exhibit a notable capacity for tumor accumulation via the improved permeability and retention effect, thereby achieving satisfactory anti-tumor PDT efficacy in a mouse subcutaneous tumor model., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

All-polymer solar cells (all-PSCs) present compelling advantages for commercial applications, including mechanical durability and optical and thermal stability. However, progress in developing high-performance polymer donors has trailed behind the emergence of excellent polymer acceptors. In this study, we report a new electron-deficient arene, fluorinated bithiophene imide (F-BTI) and its polymer donor SA1, in which two fluorine atoms are introduced at the outer β-positions in the thiophene rings of BTI to fine-tune the energy levels and aggregation of the resulting polymers. SA1 exhibits a deep HOMO level of -5.51 eV, a wide bandgap of 1.81 eV and suitable miscibility with the polymer acceptor. Polymer chains incorporating F-BTI result in a highly ordered π-π stacking and favorable phase-separated morphology within the all-polymer active layer. Thus, SA1 : PY-IT-based all-PSCs exhibit an efficiency of 16.31 % with excellent stability, which is further enhanced to a record value of 19.33 % (certified: 19.17 %) by constructing ternary device. This work demonstrates that F-BTI offers an effective route for developing new polymer materials with improved optoelectronic properties, and the emergence of F-BTI will change the scenario in terms of developing polymer donor for high-performance and stable all-PSCs., (© 2024 Wiley-VCH GmbH.)

Oxygen reduction reaction (ORR) electrocatalysts are essential for widespread application of quasi-solid-state Zn-air batteries (ZABs), but the well-known Fe-N-C single-atom catalysts (SACs) suffer from low activity and stability because of unfavorable strong adsorption of oxygenated intermediates. Herein, the study synthesizes dual Fe/I single atoms anchored on N-doped carbon nanorods (Fe/I-N-CR) via a metal-organic framework (MOF)-mediated two-step tandem-pyrolysis method. Atomic-level I doping modulates the electronic structure of Fe-N x centers via the long-range electron delocalization effect. Benefitting from the synergistic effect of dual Fe/I single-atom sites and the structural merits of 1D nanorods, the Fe/I-N-CR catalyst shows excellent ORR activity and stability, superior to Pt/C and Fe or I SACs. When the Fe/I-N-CR is employed as cathode for quasi-solid-state ZABs, a high power density of 197.9 mW cm -2 and an ultralong cycling lifespan of 280 h at 20 mA cm -2 are both achieved, greatly exceeding those of commercial Pt/C+IrO 2 (119.1 mW cm -2 and 47 h). In addition, wide-temperature adaptability and superior stability from -40 to 60 °C are realized for the Fe/I-N-CR-based quasi-solid-state ZABs. This work provides a MOF-mediated two-step tandem-pyrolysis strategy to engineer high-performance dual SACs with metal/nonmetal centers for ORR and sustainable ZABs., (© 2024 Wiley‐VCH GmbH.)

Recently, unconventional antiferromagnets that enable the spin splitting (SS) of electronic states have been theoretically proposed and experimentally realized, where the magnetic sublattices containing moments pointing at different directions are connected by a novel set of symmetries. Such SS is substantial, k-dependent, and independent of the spin-orbit coupling (SOC) strength, making these magnets promising materials for antiferromagnetic spintronics. Here, combined with angle-resolved photoemission spectroscopy (ARPES) and density functional theory (DFT) calculations, a systematic study on CrSb, a metallic spin-split antiferromagnet candidate with Néel temperature T N = 703 K, is conducted. The data reveal the electronic structure of CrSb along both out-of-plane and in-plane momentum directions, rendering an anisotropic k-dependent SS that agrees well with the calculational results. The magnitude of such SS reaches up to at least 0.8 eV at non-high-symmetry momentum points, which is significantly higher than the largest known SOC-induced SS. This compound expands the choice of materials in the field of antiferromagnetic spintronics and is likely to stimulate subsequent investigations of high-efficiency spintronic devices that are functional at room temperature., (© 2024 The Author(s). Advanced Science published by Wiley‐VCH GmbH.)

The solar-driven overall water splitting (2H 2 O→2H 2 + O 2 ) is considered as one of the most promising strategies for reducing carbon emissions and meeting energy demands. However, due to the sluggish performance and high H 2 cost, there is still a big gap for the current photocatalytic systems to meet the requirements for practical sustainable H 2 production. Economic feasibility can be attained through simultaneously generating products of greater value than O 2 , such as hydrogen peroxide (H 2 O 2 , 2H 2 O→H 2 + H 2 O 2 ). Compared with overall water splitting, this approach is more kinetically feasible and generates more high-value products of H 2 and H 2 O 2 . In several years, there has been an increasing surge in exploring the possibility and substantial progress has been achieved. In this review, a concise overview of the importance and underlying principles of PIWS is first provided. Next, the reported typical photocatalysts for PIWS are discussed, including commonly used semiconductors and cocatalysts, essential design features of these photocatalysts, and connections between their structures and activities, as well as the selected approaches for enhancing their stability. Then, the techniques used to quantify H 2 O 2 and the operando characterization techniques that can be employed to gain a thorough understanding of the reaction mechanisms are summarized. Finally, the current existing challenges and the direction needing improvement are presented. This review aims to provide a thorough summary of the most recent research developments in PIWS and sets the stage for future advancements and discoveries in this emerging area., (© 2024 Wiley‐VCH GmbH.)

In this review, the recent development of blue perovskite light-emitting diodes (PeLED) are summarized. On deep-blue (≤465 nm) perovskite nanomaterials of different structural forms are mainly focused, including nanocrystals (NCs), quantum dots (QDs), nanoplatelets (NPLs), quasi-2D thin film, 3D bulk thin film, as well as lead-free perovskite nanomaterials. The current challenges are also examined in producing efficient deep-blue PeLED, such as material and spectral instability, imbalance charge transport, Joule heat impact, and poor optoelectronic performance. Several strategies are further discussed to overcome these challenges and achieve efficient deep-blue PeLED for next-generation display technology., (© 2024 The Author(s). Advanced Materials published by Wiley‐VCH GmbH.)

0D hybrid metal halides (0D HMHs) with fully isolated inorganic units provide an ideal platform for studying the correlations between chiroptical activities and crystal structures at atomic levels. Here, through the incorporation of different solvent molecules, a series of 0D chiral manganese bromides (RR/SS-C 20 H 28 N 2 ) 3 MnBr 8 ·2X (X = C 2 H 5 OH, CH 3 OH, or H 2 O) are synthesized to elucidate their chiroptical properties. They show negligible circular dichroism signals of Mn absorptions due to C 2v -symmetric [MnBr 4 ] 2- tetrahedra. However, they display distinct circularly polarized luminescence (CPL) signals with continuously increased luminescence asymmetry factors (g lum ) from 10 -4 (X = C 2 H 5 OH) to 10 -3 (X = H 2 O). The increased g lum value is structurally revealed to originate from the enhancement of [MnBr 4 ] 2- tetrahedral bond-angle distortions, due to the presence of different solvent molecules. Furthermore, (RR/SS-C 20 H 28 N 2 )MnBr 4 ·H 2 O enantiomers with larger bond-angle distortions of [MnBr 4 ] 2- tetrahedra are synthesized based on hydrobromic acid-induced structural transformation of (RR/SS-C 20 H 28 N 2 ) 3 MnBr 8 ·2H 2 O enantiomers. Therefore, such (RR/SS-C 20 H 28 N 2 )MnBr 4 ·H 2 O enantiomers exhibit enhanced CPL signals with |g lum | up to 1.23 × 10 -2 . This work provides unique insight into enhancing chiroptical activities in 0D HMH systems., (© 2024 Wiley‐VCH GmbH.)

A new approach to control the n-doping reaction of organic semiconductors is reported using surface-functionalized gold nanoparticles (f-AuNPs) with alkylthiols acting as the catalyst only upon mild thermal activation. To demonstrate the versatility of this methodology, the reaction of the n-type dopant precursor N-DMBI-H with several molecular and polymeric semiconductors at different temperatures with/without f-AuNPs, vis-à-vis the unfunctionalized catalyst AuNPs, was investigated by spectroscopic, morphological, charge transport, and kinetic measurements as well as, computationally, the thermodynamic of catalyst activation. The combined experimental and theoretical data demonstrate that while f-AuNPs is inactive at room temperature both in solution and in the solid state, catalyst activation occurs rapidly at mild temperatures (~70 °C) and the doping reaction completes in few seconds affording large electrical conductivities (~10-140 S cm -1 ). The implementation of this methodology enables the use of semiconductor+dopant+catalyst solutions and will broaden the use of the corresponding n-doped films in opto-electronic devices such as thin-film transistors, electrochemical transistors, solar cells, and thermoelectrics well as guide the design of new catalysts., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

The construction of large and complex supramolecular architectures through self-assembly is at the forefront of contemporary coordination chemistry. Notwithstanding great success in various systems using anionic bridges (e.g., O 2- or S 2- ) or organic ligands (e.g., pyridine or carboxylate ligands), the assembly of large cyanide-bridged clusters with increasing nuclearity remains a formidable synthetic challenge. In this study, it is achieved in preparing two heterometallic cyanometallate clusters with unprecedented complexity, [Fe 20 Co 20 ] (1) and [Fe 12 Co 15 ] (2), by creating the "flexibility" through a versatile ligand of bis((1H-imidazol-4-yl)methylene)hydrazine (H 2 L) and low-coordinate cobalt. Complex 1 features a super-square array of four cyanide-bridged [Fe 4 Co 4 ] cube subunits as the corners that are interconnected by four additional [FeCo] units, resulting in a torus-shaped architecture. Complex 2 contains a lantern-like core-shell cluster with a triple-helix kernel of [Co 3 L 3 ] enveloped by a [Fe 12 Co 12 ] shell. The combined structure analysis and mass spectrometry study reveal a hierarchical assembly mechanism, which sheds new light on constructing cyanometallate nanoclusters with atomic precision. Moreover, complex 1 undergoes a thermally induced electron-transfer-coupled spin transition (ETCST) between the diamagnetic {Fe II LS } and paramagnetic {Fe III LS } configurations (LS = low spin, HS = high spin) above room temperature, representing the largest molecule displaying electron transfer and spin transition characteristic.III LS (µ-CN)Co II HS } configurations (LS = low spin, HS = high spin) above room temperature, representing the largest molecule displaying electron transfer and spin transition characteristic., (© 2024 The Author(s). Advanced Science published by Wiley‐VCH GmbH.)

The chemistry of quinone methides formed in situ has been flourishing in recent years. In sharp contrast, the development and utilization of biphenyl quinone methides are rare. In this study, we achieved a remote stereocontrolled 1,12-conjugate addition of biphenyl quinone methides formed in situ for the first time. In the presence of a suitable chiral phosphoric acid, alkynyl biphenyl quinone methides were generated from α-[4-(4-hydroxyphenyl)phenyl]propargyl alcohols, followed by enantioselective 1,12-conjugate addition with indole-2-carboxylates. The strategy enabled the alcohols to serve as efficient allenylation reagents, providing practical access to a broad range of axially chiral allenes bearing a (1,1'-biphenyl)-4-ol unit, which were previously less accessible. Combined with control experiments, density functional theory calculations shed light on the reaction mechanism, indicating that enantioselectivity originates from the nucleophilic addition of alkynyl biphenyl quinone methides. Notably, not only the presence of biphenyl quinone methides as versatile intermediates was confirmed but also organocatalytic enantioselective 1,12-addition was established., (© 2024 Wiley-VCH GmbH.)

Ordered pore engineering that embeds uniform pores with periodic alignment in electrocatalysts opens up a new avenue for achieving further performance promotion. Hierarchically ordered porous metal-organic frameworks (HOP-MOFs) possessing multilevel pores with ordered distribution are the promising precursors for the exploration of ordered porous electrocatalysts, while the scalable acquisition of HOP-MOFs with editable components and adjustable pore size regimes is critical. This review presents recent progress on hierarchically ordered pore engineering of MOF-based materials for enhanced electrocatalysis. The synthetic strategies of HOP-MOFs with different pore size regimes, including the self-assembly guided by reticular chemistry, surfactant, nanoemulsion, and nanocasting, are first introduced. Then the applications of HOP-MOFs as the precursors for exploring hierarchically ordered porous electrocatalysts are summarized, selecting representatives to highlight the boosted performance. Especially, the intensification of molecule and ion transport integrated with optimized electron transfer and site exposure over the hierarchically ordered porous derivatives are emphasized to clarify the directional transfer and integration effect endowed by ordered pore engineering. Finally, the remaining scientific challenges and an outlook of this field are proposed. It is hoped that this review will guide the hierarchically ordered pore engineering of nanocatalysts for boosting the catalytic performance and promoting the practical applications., (© 2024 Wiley‐VCH GmbH.)

Aqueous solvents in Zn metal batteries inevitably induces hydrogen evolution reactions (HER) due to fluctuating pH levels in electrolytes, leading to severe side reactions and dendrite growth. To address these challenges, buffering agents have been recently proposed as a solution to maintain constant electrolyte pH values upon cycling. Nonetheless, the critical role of buffering additives' premier pH in determining interface stability is largely overlooked. Herein, two types of buffering agents, single amphoteric and conjugate acid-base pairs, are employed to correlate their initial pHs with the interface stability. Based on the observations, the lifetime of Zn metal anodes initially increases and then decreases as the initial pH level goes up from 2.0 to 5.0, with an optimal lifetime at pH 3.3 for both buffering agent categories. This phenomenon lies in ample H + in low pH and rich OH - in high pH, leading to either severe HER or by-products passivation layer. The optimized pH allows cells to deliver a high average Coulombic efficiency of 99.61% over 1500 cycles at a large current density of 5 mA cm -2 , which is significantly superior to 345 cycles achieved in the pristine electrolyte. Furthermore, this enhanced interface enables stable Zn/activated carbon full batteries over 15 000 cycles., (© 2024 Wiley‐VCH GmbH.)

Single-atom catalysts (SACs) are considered prominent materials in the field of catalysis due to their high metal atom utilization and selectivity. However, the wide-ranging applications of SACs remain a significant challenge due to their complex preparation processes. Here, a universal strategy is reported to prepare a series of noble metal single atoms on different non-noble metal oxides through a facile one-step thermal decomposition of molten salts. By using a mixture of non-noble metal nitrate and a small-amount noble metal chloride as the precursor, noble metal single atoms can be easily introduced into the non-noble metal oxide lattice owing to the cation exchange in the in situ formed molten salt, followed by the thermal decomposition of nitrate anions during the heating process. Analyses using aberration-corrected high-angle annular dark-field scanning transmission electron microscopy and extended X-ray absorption fine structure spectroscopy confirm the formation of the finely dispersed single atoms. Specially, the as-synthesized Ir single atoms (10.97 wt%) and Pt single atoms (4.60 wt%) on the Co 3 O 4 support demonstrate outstanding electrocatalytic activities for oxygen evolution reaction and hydrogen evolution reaction, respectively., (© 2024 Wiley‐VCH GmbH.)

The semiconductor thin film engineering technique plays a key role in the development of advanced electronics. Printing uniform nanofilms on freeform surfaces with high efficiency and low cost is significant for actual industrialization in electronics. Herein, a high-throughput colloidal printing (HTCP) strategy is reported for fabricating large-area and uniform semiconductor nanofilms on freeform surfaces. High-throughput and uniform printing rely on the balance of atomization and evaporation, as well as the introduced thermal Marangoni flows of colloidal dispersion, that suppresses outward capillary flows. Colloidal printing with in situ heating enables the fast fabrication of large-area semiconductor nanofilms on freeform surfaces, such as SiO 2 /Si, Al 2 O 3 , quartz glass, poly(ethylene terephthalate) (PET), Al foil, plastic tube, and Ni foam, expanding their technological applications where substrates are essential. The printed SnS 2 nanofilms are integrated into thin-film semiconductor gas sensors with one of the fastest responses (8 s) while maintaining the highest sensitivity (R g /R a = 21) (toward 10 ppm NO 2 ), as well as an ultralow limit of detection (LOD) of 46 ppt. The ability to print uniform semiconductor nanofilms on freeform surfaces with high-throughput promises the development of next-generation electronics with low cost and high efficiency., (© 2024 Wiley‐VCH GmbH.)

Ultraviolet circularly polarized luminescence (UV-CPL) with high photon energy shows great potential in polarized light sources and stereoselective photopolymerization. However, developing luminescent materials with high UV-CPL performance remains challenging. Here, we report a pair of rare earth Ce 3+ -based zero-dimensional (0D) chiral hybrid metal halides (HMHs), R/S-(C 14 H 24 N 2 ) 2 CeBr 7 , which exhibits characteristic UV emissions derived from the Ce 5d-4f transition. The compounds show simultaneously high photoluminescent quantum yields of (32-39)% and large luminescent dissymmetry factor (|g lum |) values of (1.3-1.5)×10 -2 . Thus, the figures of merits of R/S-(C 14 H 24 N 2 ) 2 CeBr 7 are calculated to be (4.5-5.8)×10 -3 , which are superior to the reported UV-CPL emissive materials. Additionally, nearly 91 % of their PL intensities at 300 K can be well preserved at 380 K (LED operating temperature) without phase transition or decomposition, demonstrating the excellent structural and optical thermal stabilities of R/S-(C 14 H 24 N 2 ) 2 CeBr 7 . Based on these enantiomers, the fabricated UV-emitting CP-LEDs exhibit high polarization degrees of ±1.0 %. Notably, the UV-CPL generated from the devices can significantly trigger the enantioselective photopolymerization of diacetylene with remarkable stereoselectivity, and consequently yield polymerized products with the anisotropy factors of circular dichroism (g CD ) up to ±3.9×10 -2 , outperforming other UV-CPL materials and demonstrating their great potential as UV-polarized light sources., (© 2024 Wiley-VCH GmbH.)

Electrochemical activation usually accompanies in situ atom rearrangement forming new catalytic sites with higher activity due to reconstructed atomic clusters or amorphous phases with abundant dangling bonds, vacancies, and defects. By harnessing the pre-catalytic process of reconstruction, a multilevel structure of CuNi alloy nanoparticles encapsulated in N-doped carbon (CuNi nanoalloy@N/C) transforms into a highly active compound of Ni-doped CuO nanocluster supported on (N/O-C) co-doped C. Both the exposure of accessible active sites and the activity of individual active sites are greatly improved after the pre-catalytic reconstruction. Manipulating the Cu/Ni ratios of CuNi nanoalloy@N/C can tailor the electronic property and d-band center of the high-active compound, which greatly optimizes the energetics of oxygen evolution reaction (OER) intermediates. This interplay among Cu, Ni, C, N, and O modifies the interface, triggers the active sites, and regulates the work functions, thereby realizing a synergistic boost in OER., (© 2024 The Authors. Advanced Science published by Wiley‐VCH GmbH.)

Due to their amorphous-like ultralow lattice thermal conductivity both below and above the superionic phase transition, crystalline Cu- and Ag-based superionic argyrodites have garnered widespread attention as promising thermoelectric materials. However, despite their intriguing properties, quantifying their lattice thermal conductivities and a comprehensive understanding of the microscopic dynamics that drive these extraordinary properties are still lacking. Here, an integrated experimental and theoretical approach is adopted to reveal the presence of Cu-dominated low-energy optical phonons in the Cu-based argyrodite Cu 7 PS 6 . These phonons yield strong acoustic-optical phonon scattering through avoided crossing, enabling ultralow lattice thermal conductivity. The Unified Theory of thermal transport is employed to analyze heat conduction and successfully reproduce the experimental amorphous-like ultralow lattice thermal conductivities, ranging from 0.43 to 0.58 W m -1 K -1 , in the temperature range of 100-400 K. The study reveals that the amorphous-like ultralow thermal conductivity of Cu 7 PS 6 stems from a significantly dominant wave-like conduction mechanism. Moreover, the simulations elucidate the wave-like thermal transport mainly results from the contribution of Cu-associated low-energy overlapping optical phonons. This study highlights the crucial role of low-energy and overlapping optical modes in facilitating amorphous-like ultralow thermal transport, providing a thorough understanding of the underlying complex dynamics of argyrodites., (© 2024 The Authors. Advanced Science published by Wiley‐VCH GmbH.)

Diluting organic semiconductors with a host insulating polymer is used to increase the electronic mobility in organic electronic devices, such as thin film transistors, while considerably reducing material costs. In contrast to organic electronics, bioelectronic devices such as the organic electrochemical transistor (OECT) rely on both electronic and ionic mobility for efficient operation, making it challenging to integrate hydrophobic polymers as the predominant blend component. This work shows that diluting the n-type conjugated polymer p(N-T) with high molecular weight polystyrene (10 KDa) leads to OECTs with over three times better mobility-volumetric capacitance product (µC*) with respect to the pristine p(N-T) (from 4.3 to 13.4 F V -1 cm -1 s -1 ) while drastically decreasing the amount of conjugated polymer (six times less). This improvement in µC* is due to a dramatic increase in electronic mobility by two orders of magnitude, from 0.059 to 1.3 cm 2 V -1 s -1 for p(N-T):Polystyrene 10 KDa 1:6. Moreover, devices made with this polymer blend show better stability, retaining 77% of the initial drain current after 60 minutes operation in contrast to 12% for pristine p(N-T). These results open a new generation of low-cost organic mixed ionic-electronic conductors where the bulk of the film is made by a commodity polymer., (© 2024 The Authors. Advanced Materials published by Wiley‐VCH GmbH.)

Thermally activated delayed fluorescence (TADF) emitters featuring through-space charge transfer (TSCT) can be excellent candidates for piezochromic luminescent (PCL) materials due to their structural dynamics. Spatial donor-acceptor (D-A) stacking arrangements enable the modulation of inter- and intramolecular D-A interactions, as well as spatial charge transfer states, under varying pressure conditions. Herein, we demonstrate an effective approach toward dynamic reversible full-color PCL materials with TSCT-TADF characteristics. Their single crystals exhibit a full-color-gamut PCL process spanning a range of 170 nm. Moreover, the TSCT-TADF-PCL emitters display a unity photoluminescence quantum yield, and show promising application in X-ray scintillator imaging., (© 2024 Wiley-VCH GmbH.)

Electrochemical ethanol oxidation is crucial to directly convert a biorenewable liquid fuel with high energy density into electrical energy, but it remains an inefficient reaction even with the best catalysts. To boost ethanol oxidation, developing multimetallic nanoalloy has emerged as one of the most effective strategies, yet faces a challenge in the rational engineering of multimetallic active-site ensembles at atomic-level. Herein, starting from typical PtCu nanocrystals, an atomic Sn diffusion strategy is developed to construct well-defined Pt 47 Sn 12 Cu 41 octopod nanoframes, which is enclosed by high-index facets of n (111)-(111), such as {331} and {221}. Pt 47 Sn 12 Cu 41 achieves a high mass activity of 3.10 A mg -1 and promotes the C-C bond breaking and oxidation of poisonous CO intermediate, representing a state-of-the-art electrocatalyst toward ethanol oxidation in acidic electrolyte. Density functional theory （DFT） calculations have confirmed that the introduction of Sn improves the electroactivity by uplifting the d-band center through the s-p-d coupling. Meanwhile, the strong binding of ethanol and the reduced energy barrier of CO oxidation guarantee a highly efficient ethanol oxidation process with improved Faradic efficiency of C1 products. This work offers a promising strategy for constructing novel multimetallic nanoalloys tailored by atomic metal sites as the efficient electrocatalysts.Pt and promotes the C-C bond breaking and oxidation of poisonous CO intermediate, representing a state-of-the-art electrocatalyst toward ethanol oxidation in acidic electrolyte. Density functional theory （DFT） calculations have confirmed that the introduction of Sn improves the electroactivity by uplifting the d-band center through the s-p-d coupling. Meanwhile, the strong binding of ethanol and the reduced energy barrier of CO oxidation guarantee a highly efficient ethanol oxidation process with improved Faradic efficiency of C1 products. This work offers a promising strategy for constructing novel multimetallic nanoalloys tailored by atomic metal sites as the efficient electrocatalysts., (© 2024 Wiley‐VCH GmbH.)

Single-atom decorating of Pt emerges as a highly effective strategy to boost catalytic properties, which can trigger the most Pt active sites while blocking the smallest number of Pt atoms. However, the rational design and creation of high-density single-atoms on Pt surface remain as a huge challenge. Herein, a customized synthesis of surface-enriched single-Bi-atoms tailored Pt nanorings (SE-Bi 1 /Pt NRs) toward methanol oxidation is reported, which is guided by the density functional theory (DFT) calculations suggesting that a relatively higher density of Bi species on Pt surface can ensure a CO-free pathway and accelerate the kinetics of *HCOOH formation. Decorating Pt NRs with dense single-Bi-atoms is achieved by starting from PtBi intermetallic nanoplates (NPs) with intrinsically isolated Bi atoms and subsequent etching and annealing treatments. The SE-Bi 1 /Pt NRs exhibit a mass activity of 23.77 A mg -1 Pt toward methanol oxidation in alkaline electrolyte, which is 2.2 and 12.8 times higher than those of Pt-Bi NRs and Pt/C, respectively. This excellent activity endows the SE-Bi 1 /Pt NRs with a high likelihood to be used as a practical anodic electrocatalyst for direct methanol fuel cells （DMFCs） with high power density of 85.3 mW cm -2 and ultralow Pt loading of 0.39 mg cm -2 ., (© 2024 Wiley‐VCH GmbH.)

High-performing n-type polymers are crucial for the advance of organic electronics field, however strong electron-deficient building blocks with optimized physicochemical properties for constructing them are still limited. The imide-functionalized polycyclic aromatic hydrocarbons (PAHs) with extended π-conjugated framework, high electron deficiency and good solubility serve as promising candidates for developing high-performance n-type polymers. Among the PAHs, phenanthrene (PhA) features a well-delocalized aromatic π-system with multiple modifiable active sites . However, the PhA-based imides are seldom studied, mainly attributed to the synthetic challenge. Herein, we report two functionalized PhAs, CPOI and CPCNI, by simultaneously incorporating imide with carbonyl or dicyanomethylene onto PhA. Notably, the dicyanomethylene-modified CPCNI exhibits a well stabilized LUMO energy level (-3.84 eV), attributed to the synergetic inductive effect from imide and cyano groups. Subsequently, based on CPOI and CPCNI, two polymers PCPOI-Tz and PCPCNI-Tz were developed. Applied to organic thin-film transistors, owing to the strong electron-deficiency of CPCNI, polymer PCPCNI-Tz shows an improved electron mobility and largely decreased threshold voltage compared with PCPOI-Tz. This work affords two structurally novel electron-deficient building blocks and highlights the effectiveness of dual functionalization of PhAs with strong electron-withdrawing groups for devising n-type polymers., (© 2024 Wiley‐VCH GmbH.)

The reversible and durable operation of sodium metal batteries at low temperatures (LT) is essential for cold-climate applications but is plagued by dendritic Na plating and unstable solid-electrolyte interphase (SEI). Current Coulombic efficiencies of sodium plating/stripping at LT fall far below 99.9%, representing a significant performance gap yet to be filled. Here, the solvation structure of the conventional 1 m NaPF 6 in diglyme electrolyte by facile cyclic ether (1,3-dioxolane, DOL) dilution is efficiently reconfigured. DOL diluents help shield the Na + -PF 6 Coulombic interaction and intermolecular forces of diglyme, leading to anomalously high Na - -ion conductivity. Besides, DOL participates in the solvation sheath and weakens the chelation of Na + -ion conductivity. Besides, DOL participates in the solvation sheath and weakens the chelation of Na + in the solvates and promotes their preferential decomposition. A desired inorganic-rich SEI is generated with compositional uniformity, high ionic conductivity, and high Young's modulus. Consequently, a record-high Coulombic efficiency over 99.9% is achieved at an ultralow temperature of -55 °C, and a 1 Ah capacity pouch cell of initial anode-free sodium metal battery retains 95% of the first discharge capacity over 100 cycles at -25 °C. This study thus provides new insights for formulating electrolytes toward increased Na reversibility at LT.6 - in the solvates and promotes their preferential decomposition. A desired inorganic-rich SEI is generated with compositional uniformity, high ionic conductivity, and high Young's modulus. Consequently, a record-high Coulombic efficiency over 99.9% is achieved at an ultralow temperature of -55 °C, and a 1 Ah capacity pouch cell of initial anode-free sodium metal battery retains 95% of the first discharge capacity over 100 cycles at -25 °C. This study thus provides new insights for formulating electrolytes toward increased Na reversibility at LT., (© 2024 Wiley‐VCH GmbH.)

Hybrid metal halides (HMHs) with efficient circularly polarized luminescence (CPL) have application prospects in many fields, due to their abundant host-guest structures and high photoluminescence quantum yield (PLQY). However, CPLs in HMHs are predominantly excited by light or electricity, limiting their use in multivariate environments. It is necessary to explore a novel excitation method to extend the application of chiral HMHs as smart stimuli-responsive optical materials. In this work, an enantiomeric pair of 0D hybrid manganese bromides, [H 2 (2R,4R)-(+)/(2S,4S)-(-)-2,4-bis(diphenylphosphino)pentane]MnBr 4 [(R/S)-1] is presented, which exhibits efficient CPL emissions with near-unity PLQYs and high dissymmetry factors of ± 2.0 × 10 -3 . Notably, (R/S)-1 compounds exhibit unprecedented and bright circularly polarized mechanoluminescence (CPML) emissions under mechanical stimulation. Moreover, (R/S)-1 possess high mechanical force sensitivities with mechanoluminescence (ML) emissions detectable under 0.1 N force stimulation. Furthermore, this ML emission exhibits an extraordinary antithermal quenching effect in the temperature range of 300-380 K, which is revealed to originate from a thermal activation energy compensation mechanism from trap levels to Mn(II) 4 T 1 level. Based on their intriguing optical properties, these compounds as chiral force-responsive materials are demonstrated in multilevel confidential information encryption., (© 2024 Wiley‐VCH GmbH.)

Conductive metal-organic frameworks (MOFs) are a type of porous material. It consists of metal ions coordinated with highly conjugated organic ligands. The high density of carriers and orbital overlap contribute to the amazing conductivity. Additionally, conductive MOFs inherit the advantages of large specific surface area, structural diversity, and adjustable pore size from MOFs. These excellent properties have attracted many researchers to explore controllable synthesis and electrochemical applications over the past decade. This work provides an overview of the recent advances in the synthesis strategies of conductive MOFs and highlights their applications in electrocatalysis, supercapacitors, sensors, and batteries. Finally, the challenges faced by the synthesis and application of conductive MOFs are discussed, as well as the views on promising solutions for them are presented., (© 2023 Wiley‐VCH GmbH.)

Developing low-cost and high-performance n-type polymer semiconductors is essential to accelerate the application of organic thermoelectrics (OTEs). To achieve this objective, it is critical to design strong electron-deficient building blocks with simple structure and easy synthesis, which are essential for the development of n-type polymer semiconductors. Herein, we synthesized two cyano-functionalized highly electron-deficient building blocks, namely 3,6-dibromopyrazine-2-carbonitrile (CNPz) and 3,6-Dibromopyrazine-2,5-dicarbonitrile (DCNPz), which feature simple structures and facile synthesis. CNPz and DCNPz can be obtained via only one-step reaction and three-step reactions from cheap raw materials, respectively. Based on CNPz and DCNPz, two acceptor-acceptor (A-A) polymers, P(DPP-CNPz) and P(DPP-DCNPz) are successfully developed, featuring deep-positioned lowest unoccupied molecular orbital (LUMO) energy levels, which are beneficial to n-type organic thin-film transistors (OTFTs) and OTEs performance. An optimal unipolar electron mobility of 0.85 and 1.85 cm 2  V -1  s -1 is obtained for P(DPP-CNPz) and P(DPP-DCNPz), respectively. When doped with N-DMBI, P(DPP-CNPz) and P(DPP-DCNPz) show high n-type electrical conductivities/power factors of 25.3 S cm -1 /41.4 μW m -1  K -2 , and 33.9 S cm -1 /30.4 μW m -1  K -2 , respectively. Hence, the cyano-functionalized pyrazine CNPz and DCNPz represent a new class of structurally simple, low-cost and readily accessible electron-deficient building block for constructing n-type polymer semiconductors., (© 2024 Wiley-VCH GmbH.)

α-Aryl substituted nitroalkanes are valuable synthetic building blocks that can be easily converted into α-aryl substituted aldehydes, ketones, carboxylic acids, as well as amines. Herein, an efficient Cu/oxalamide-catalyzed coupling between nitroalkanes and (hetero)aryl halides (Br, I) was developed to direct access highly diverse α-aryl substituted nitroalkanes. Compared with the current state of art, this protocol is more environmentally friendly and practical for synthetic chemists. This approach is characterized by a broad substrate scope on both nitroalkane part (primary nitroalkanes and nitromethane) and sp 2 halide part ((hetero)aryl bromides/iodides and alkenyl bromides/iodides). The excellent functional group tolerance was observed, which would enable real world synthetic applications. More importantly, TON of current transformation reached to 3640, when some aryl iodides were used as coupling partners. This represents currently the highest catalyst turnover for transition-metal catalyzed α-arylation of nitroalkanes. Furthermore, the successful application in late-stage modification of complex molecules and synthesis of a known retinoid X receptor (RXR) antagonist exemplified its synthetic potential., (© 2023 Wiley-VCH GmbH.)

Exploration of new electron-withdrawing building blocks plays a key role in the development of n-type organic semiconductors. Herein, a strong electron-withdrawing building block, dipyridyl-fused quinoxalineimide (DPQI), was successfully designed and synthesized. Single-crystal structure reveals that DPQI molecule possesses a completely planar backbone, which is beneficial for charge transport. For comparison, dibenzo-fused quinoxalineimide (DBQI) was also synthesized. The frontier molecular orbital (FMO) energy levels downshift with the incorporation of nitrogen atoms onto the π-conjugated backbone of quinoxalineimide. Two acceptor-acceptor (or all-acceptor) polymers P(BTI-DBQI) and P(BTI-DPQI) based on DBQI and DPQI were synthesized, respectively. Two polymers exhibit deep lowest-unoccupied molecular orbital (LUMO) levels (~-3.5 eV). Additionally, P(BTI-DPQI) exhibits unipolar n-type charge transport with μ e of 1.4×10 -4  cm 2  V -1  s -1 in the organic field-effect transistors (OFET), which render them highly attractive for developing n-type semiconductors device. This work demonstrates that DPQI is a promising building block for constructing n-type polymer semiconductors., (© 2023 Wiley-VCH GmbH.)

Developing polymers with high electrical conductivity (σ) after n-doping is a great challenge for the advance of the field of organic thermoelectrics (OTEs). Herein, we report a series of thiazole imide-based n-type polymers by gradually increasing selenophene content in polymeric backbone. Thanks to the strong intramolecular noncovalent N⋅⋅⋅S interaction and enhanced intermolecular Se⋅⋅⋅Se interaction, with the increase of selenophene content, the polymers show gradually lowered LUMOs, more planar backbone, and improved film crystallinity versus the selenophene-free analogue. Consequently, polymer PDTzSI-Se with the highest selenophene content achieves a champion σ of 164.0 S cm -1 and a power factor of 49.0 μW m -1  K -2 in the series when applied in OTEs after n-doping. The σ value is the highest one for n-type donor-acceptor OTE materials reported to date. Our work indicates that selenophene substitution is a powerful strategy for developing high-performance n-type OTE materials and selenophene incorporated thiazole imides offer an excellent platform in enabling n-type polymers with high backbone coplanarity, deep-lying LUMO and enhanced mobility/conductivity., (© 2023 Wiley-VCH GmbH.)

Structural dimensionality and electronic dimensionality play a crucial role in determining the type of excitonic emission in hybrid metal halides (HMHs). It is important but challenging to achieve free exciton (FE) emission in zero-dimensional (0D) HMHs based on the control over the electronic dimensionality. In this work, a quasi-0D HMH (C 7 H 15 N 2 Br) 2 PbBr 4 with localized electronic dimensionality is prepared as a prototype model. With increasing pressure onto (C 7 H 15 N 2 Br) 2 PbBr 4 , the broad and weak self-trapped exciton (STE) emission at ambient conditions is considerably enhanced before 3.6 GPa, which originates from more distorted [PbBr 4 ] 2- seesaw units upon compression. Notably, a narrow FE emission in (C 7 H 15 N 2 Br) 2 PbBr 4 appears at 3.6 GPa, and then this FE emission is gradually strengthened up to 8.4 GPa. High pressure structural characterizations reveal that anisotropic contraction of (C 7 H 15 N 2 Br) 2 PbBr 4 results in a noticeable reduction in the distance between adjacent [PbBr 4 ] 2- seesaw units, as well as an obvious enhancement of crystal stiffness. Consequently, the electronic connectivity in (C 7 H 15 N 2 Br) 2 PbBr 4 is sufficiently promoted above 3.6 GPa, which is also supported with theoretical calculations. The elevation of electronic connectivity and enhanced stiffness together lead to pressure-induced FE emission and subsequent emission enhancement in quasi-0D (C 7 H 15 N 2 Br) 2 PbBr 4 ., (© 2023 Wiley-VCH GmbH.)

High-performance n-type polymeric mixed ionic-electronic conductors (PMIECs) are essential for realizing organic electrochemical transistors (OECTs)-based low-power complementary circuits and biosensors, but their development still remains a great challenge. Herein, by devising two novel n-type polymers (f-BTI2g-SVSCN and f-BSeI2g-SVSCN) containing varying selenophene contents together with their thiophene-based counterpart as the control, it is demonstrated that gradually increasing selenophene loading in polymer backbones can simultaneously yield lowered lowest unoccupied molecular orbital levels, boosted charge-transport properties, and improved ion-uptake capabilities. Therefore, a remarkable volumetric capacitance (C*) of 387.2 F cm -3 and a state-of-the-art OECT electron mobility (µ e,OECT ) of 0.48 cm 2 V -1 s -1 are synchronously achieved for f-BSeI2g-SVSCN having the highest selenophene content, yielding an unprecedented geometry-normalized transconductance (g m,norm ) of 71.4 S cm -1 and record figure of merit (µC*) value of 191.2 F cm -1 V -1 s -1 for n-type OECTs. Thanks to such excellent performance of f-BSeI2g-SVSCN-based OECTs, a glucose sensor with a remarkably low detection limit of 10 nMm and decent selectivity is further implemented, demonstrating the power of selenophene substitution strategy in enabling high-performance n-type PMIECs for biosensing applications., (© 2023 Wiley-VCH GmbH.)

The limited conductivity of existing transparent conducting oxide (TCO) greatly restricts the further performance improvement of perovskite solar cells (PSCs), especially for large-area devices. Herein, buried-metal-grid tin-doped indium oxide (BMG ITO) electrodes are developed to minimize the power loss caused by the undesirable high sheet resistance of TCOs. By burying 140-nm-thick metal grids into ITO using a photolithography technique, the sheet resistance of ITO is reduced from 15.0 to 2.7 Ω sq -1 . The metal step of BMG over ITO has a huge impact on the charge carrier transport in PSCs. The PSCs using BMG ITO with a low metal step deliver power conversion efficiencies (PCEs) significantly better than that of their counterparts with higher metal steps. Moreover, compared with the pristine ITO-based PSCs, the BMG ITO-based PSCs show a smaller PCE decrease when scaling up the active area of devices. The parallel-connected large-area PSCs with an active area of 102.8 mm 2 reach a PCE of 22.5%. The BMG ITO electrodes are also compatible with the fabrication of inverted-structure PSCs and organic solar cells. The work demonstrates the great efficacy of improving the conductivity of TCO by BMG and opens up a promising avenue for constructing highly efficient large-area PSCs., (© 2023 Wiley-VCH GmbH.)

Developing high-performance n-type polymer mixed ionic-electronic conductors (PMIECs) is a grand challenge, which largely determines their applications in vaious organic electronic devices, such as organic electrochemical transistors (OECTs) and organic thermoelectrics (OTEs). Herein, two halogen-functionalized PMIECs f-BTI2g-TVTF and f-BTI2g-TVTCl built from fused bithiophene imide dimer (f-BTI2) as the acceptor unit and halogenated thienylene-vinylene-thienylene (TVT) as the donor co-unit are reported. Compared to the control polymer f-BTI2g-TVT, the fluorinated f-BTI2g-TVTF shows lower-positioned lowest unoccupied molecular orbital (LUMO), improved charge transport property, and greater ion uptake capacity. Consequently, f-BTI2g-TVTF delivers a state-of-the-art µC* of 90.2 F cm -1 V -1 s -1 with a remarkable electron mobility of 0.41 cm 2 V -1 s -1 in OECTs and an excellent power factor of 64.2 µW m -1 K -2 in OTEs. An OECT-based inverter amplifier is further demonstrated with voltage gain up to 148 V V -1 , which is among the highest values for OECT inverters. Such results shed light on the impacts of halogen atoms on developing high-performing n-type PMIECs., (© 2023 Wiley-VCH GmbH.)

Two dimensional (2D) hybrid metal halides (HMHs) usually exhibit free excitonic (FE) emission, and self-trapped excitonic (STE) emission can also be achieved by adopting appropriate halogens and organic cations. Recently, significant efforts have been made to modulate and then clarify the transformation and connection between these two types of excitonic emissions in 2D HMHs. In this study, intriguing pressure-tuned transitions between FE emission and STE emission are observed in 2D (C 7 H 7 N 2 ) 2 PbCl 4 . In contrast, only FE emissions with tunable emission energies are observed in 2D (C 7 H 7 N 2 ) 2 PbBr 4 which possesses a similar structure with (C 7 H 7 N 2 ) 2 PbCl 4 under compression. Such distinct halide-dependent optical responses under pressure are experimentally revealed to arise from the intricate interplay among several factors in these HMHs, including the stiffness of the structure, the Coulomb force between the organic cations and the inorganic octahedra, and the magnitude of inorganic octahedral distortion. These high-pressure optical explorations can unravel the underlying interrelationship between the crystal structure and excitonic emission in 2D HMHs., (© 2023 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Urea synthesis from abundant CO 2 and N-feedstocks via renewable electricity has attracted increasing interests, offering a promising alternative to the industrial-applied Haber-Meiser process. However, the studies toward electrochemical urea production remain scarce and appeal for more research. Herein, in this perspective, an up-to-date overview on the urea electrosynthesis is highlighted and summarized. Firstly, the reaction pathways of urea formation through various feedstocks are comprehensively discussed. Then, we focus on the strategies of materials design to improve C-N coupling efficiency by identifying the descriptor and understanding the reaction mechanism. Finally, the current challenges and disadvantages in this field are reviewed and some future development directions of electrocatalytic urea synthesis are also prospected. This Minireview aims to promote future investigations of the electrochemical urea synthesis., (© 2023 Wiley-VCH GmbH.)

The shortage of narrow band gap polymer acceptors with high electron mobility is the major bottleneck for developing efficient all-polymer solar cells (all-PSCs). Herein, we synthesize a distannylated electron-deficient biselenophene imide monomer (BSeI-Tin) with high purity/reactivity, affording an excellent chance to access acceptor-acceptor (A-A) type polymer acceptors. Copolymerizing BSeI-Tin with dibrominated monomer Y5-Br, the resulting A-A polymer PY5-BSeI shows a higher molecular weight, narrower band gap, deeper-lying frontier molecular orbital levels and larger electron mobility than the donor-acceptor type counterpart PY5-BSe. Consequently, the PY5-BSeI-based all-PSCs deliver a remarkable efficiency of 17.77 % with a high short-circuit current of 24.93 mA cm -2 and fill factor of 75.83 %. This efficiency is much higher than that (10.70 %) of the PY5-BSe-based devices. Our study demonstrates that BSeI is a promising building block for constructing high-performance polymer acceptors and stannylation of electron-deficient building blocks offers an excellent approach to developing A-A type polymers for all-PSCs and even beyond., (© 2023 Wiley-VCH GmbH.)

Developing high-performance but low-cost n-type polymers remains a significant challenge in the commercialization of organic field-effect transistors (OFETs). To achieve this objective, it is essential to design the key electron-deficient units with simple structures and facile preparation processes, which can facilitate the production of low-cost n-type polymers. Herein, by sequentially introducing fluorine and cyano functionalities onto trans-1,3-butadiene, we developed a series of structurally simple but highly electron-deficient building blocks, namely 1,4-dicyano-butadiene (CNDE), 3-fluoro-1,4-dicyano-butadiene (CNFDE), and 2,3-difluoro-1,4-dicyano-butadiene (CNDFDE), featuring a highly coplanar backbone and deep-positioned lowest unoccupied molecular orbital (LUMO) energy levels (-3.03-4.33 eV), which render them highly attractive for developing n-type semiconducting polymers. Notably, all these electron-deficient units can be easily accessed by a two-step high-yield synthetic procedure from low-cost raw materials, thus rendering them highly promising candidates for commercial applications. Upon polymerization with diketopyrrolopyrrole (DPP), three copolymers were developed that demonstrated unipolar n-type transport characteristics in OFETs with the highest electron mobility of >1 cm 2  V -1  s -1 . Hence, CNDE, CNFDE, and CNDFDE represent a class of novel, simple, and efficient electron-deficient units for constructing low-cost n-type polymers, thereby providing valuable insight for OFET applications., (© 2023 Wiley-VCH GmbH.)

Chiral zero-dimensional hybrid metal halides (0D HMHs) could combine excellent optical properties and chirality, making them promising for circularly polarized luminescence (CPL). However, chiral 0D HMHs with efficient CPL have been rarely reported. Here, we propose an efficient strategy to achieve simultaneously high photoluminescence quantum yield (PLQY) and large dissymmetry factor (g lum ), by integrating achiral and chiral ligands into 0D HMHs. Specifically, three pairs of chiral 0D hybrid indium-antimony chlorides are synthesized by combing achiral guanidine with three types of chiral methylbenzylammonium-based derivatives as the organic cations. These chiral 0D HMHs exhibit near-unity PLQY and large g lum values up to around ±1×10 -2 . The achiral guanidine ligand is not only essential to crystallize these hybrid indium-antimony chlorides to achieve near-unity PLQYs, but also greatly enhances the chirality induction from organic ligands to inorganic units in these 0D HMHs. Furthermore, the choice of different chiral ligands can modify the strength of hydrogen bonding interactions in these 0D HMHs, to maximize their g lum values. Overall, this study provides a robust way to realize efficient CPL in chiral HMHs, expanding their applications in chiroptical fields., (© 2023 Wiley-VCH GmbH.)

The buried interface in perovskite solar cells (PSCs) is pivotal for achieving high efficiency and stability. However, it is challenging to study and optimize the buried interface due to its non-exposed feature. Here, a facile and effective strategy is developed to modify the SnO 2 /perovskite buried interface by passivating the buried defects in perovskite and modulating carrier dynamics via incorporating formamidine oxalate (FOA) in SnO 2 nanoparticles. Both formamidinium and oxalate ions show a longitudinal gradient distribution in the SnO 2 layer, mainly accumulating at the SnO 2 /perovskite buried interface, which enables high-quality upper perovskite films, minimized defects, superior interface contacts, and matched energy levels between perovskite and SnO 2 . Significantly, FOA can simultaneously reduce the oxygen vacancies and tin interstitial defects on the SnO 2 surface and the FA + /Pb 2+ associated defects at the perovskite buried interface. Consequently, the FOA treatment significantly improves the efficiency of the PSCs from 22.40% to 25.05% and their storage- and photo-stability. This method provides an effective target therapy of buried interface in PSCs to achieve very high efficiency and stability., (© 2023 Wiley-VCH GmbH.)

The engineering of intermolecular interaction is challenging but critical for magnetically switchable molecules. Here, we prepared two cyanide-bridged [Fe 4 Co 4 ] cube complexes via the alkynyl- and alcohol-functionalized trispyrazoyl capping ligands. The alkynyl-functionalized complex 1 exhibited a thermally-induced incomplete metal-to-metal electron transfer (MMET) behaviour at around 220 K, while the mixed alkynyl/alcohol-functionalized cube of 2 showed a complete and abrupt MMET behaviour at 232 K. Remarkably, both compounds showed a long-lived photo-induced metastable state up to 200 K. The crystallographic study demonstrated that the incomplete transition of 1 was likely due to the possible elastic frustration originating from the competition between the anion-propagated elastic interactions and inter-cluster alkynyl-alkynyl & CH-alkynyl interactions, whereas the latter are eliminated in 2 as a result of the partial substitution by the alcohol-functionalized ligand. Additionally, the introduction of chemically distinguishable cobalt centers within the cube unit of 2 did not lead to a two-step but a one-step transition, possibly because of the strong ferroelastic intramolecular interaction through the cyanide bridges., (© 2023 Wiley-VCH GmbH.)

High-concentrated non-flammable electrolytes (HCNFE) in lithium metal batteries prevent thermal runaway accidents, but the microstructure of their solid electrolyte interphase (SEI) remains largely unexplored, due to the lack of direct imaging tools. Herein, cryo-HRTEM is applied to directly visualize the native state of SEI at the atomic scale. In HCNFE, SEI has a uniform laminated crystalline-amorphous structure that can prevent further reaction between the electrolyte and lithium. The inorganic SEI component, Li 2 S 2 O 7 , is precisely identified by cryo-HRTEM. Density functional theory (DFT) calculations demonstrate that the final Li 2 S 2 O 7 phase has suitable natural transmission channels for Li-ion diffusion and excellent ionic conductivity of 1.2 × 10 -5 S cm -1 ., (© 2023 Wiley-VCH GmbH.)

The practical application of Zn metal anodes in electronic devices is hindered by dendrite growth and parasitic reactions. Electrolyte optimization, particularly the introduction of organic co-solvents, is widely used to circumvent these challenges. Various organic solvents in a wide range of concentrations have been reported; however, their influences and corresponding working mechanisms at different concentrations are largely unexplored in the same organic species. Herein, economical, low-flammable ethylene glycol (EG) is used as a model co-solvent in aqueous electrolytes to examine the relationship between its concentration, anode-stabilizing effect, and mechanism. Two maximal values are observed for the lifetime of Zn/Zn symmetric batteries under EG concentrations from 0.05 vol% to 48 vol%. Zn metal anodes can stably run for over 1700 h at a low EG content (0.25 vol%) and high EG content (40 vol%). Based on the complementary experimental and theoretical calculations, the enhancements in low- and high-content EG are ascribed to the specific surface adsorption for suppressed dendrite growth and the regulated solvation structure for inhibited side reactions, respectively. Intriguingly, a similar concentration-reliant bimodal phenomenon is observed in other low-flammable organic solvents (e.g., glycerol and dimethyl sulfoxide), thereby suggesting universality of this study and providing insight into electrolyte optimization., (© 2023 Wiley-VCH GmbH.)

Multifunctional nanoaggregates are widely used in cancer phototheranostics. However, it is challenging to construct their multifunctionality with a single component, and deliver them rapidly and efficiently without complex modifications. Herein, a NIR-absorbing small molecule named TBT-2(TP-DPA) is designed and certify its theranostic potentials. Then, their nanoaggregates, which are simply encapsulated by DSPE-PEG, demonstrate a photothermal efficiency of 51% while keeping a high photoluminescence quantum yield in the NIR region. Moreover, the nanoaggregates can be excited and delivered by an 808 nm pulse laser to solid tumors within only 40 min. The delivery efficiency and theranostic efficacy are better than that of the traditional enhanced permeability and retention (EPR) effect (generally longer than 24 hours). This platform is first termed as the photoinduced thermoacoustic (PTA) process, and confirm its application requires both NIR-responsive materials and pulse laser irradiation. This study not only inspires the design of multifunctional nanoaggregates, but also offers a feasible approach to their fast delivery. The platform reported here provides a promising prospect to boost the development of multifunctional theranostic drugs and maximize the efficacy of used medicines for their clinical applications., (© 2023 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Current state-of-the-art in situ transmission electron microscopy (TEM) characterization technology has been capable of statically or dynamically nanorobotic manipulating specimens, affording abundant atom-level material attributes. However, an insurmountable barrier between material attributes investigations and device-level application explorations exists due to immature in situ TEM manufacturing technology and sufficient external coupled stimulus. These limitations seriously prevent the development of in situ device-level TEM characterization. Herein, a representative in situ opto-electromechanical TEM characterization platform is put forward by integrating an ultra-flexible micro-cantilever chip with optical, mechanical, and electrical coupling fields for the first time. On this platform, static and dynamic in situ device-level TEM characterizations are implemented by utilizing molybdenum disulfide (MoS 2 ) nanoflake as channel material. E-beam modulation behavior in MoS 2  transistors is demonstrated at ultra-high e-beam acceleration voltage (300 kV), stemming from inelastic scattering electron doping into MoS 2  nanoflakes. Moreover, in situ dynamic bending MoS 2  nanodevices without/with laser irradiation reveals asymmetric piezoresistive properties based on electromechanical effects and secondary enhanced photocurrent based on opto-electromechanical coupling effects, accompanied by real-time monitoring atom-level characterization. This approach provides a step toward advanced in situ device-level TEM characterization technology with excellent perception ability and inspires in situ TEM characterization with ultra-sensitive force feedback and light sensing., (© 2023 Wiley-VCH GmbH.)

Poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA) represents the state-of-the-art hole transport material (HTM) in inverted perovskite solar cells (PSCs). However, unsatisfied surface properties of PTAA and high energy disorder in the bulk film hinder the further enhancement of device performance. Herein, a simple small molecule 10-(4-(3,6-dimethoxy-9H-carbazol-9-yl)phenyl)-3,7-bis(4-vinylphenyl)-10H-phenoxazine (MCz-VPOZ) is strategically developed for in situ fabrication of polymer hole conductor (CL-MCz) via a facile and low-temperature cross-linking technology. The resulting polymer CL-MCz offers high energy ordering and improved electrical conductivity, as well as appropriate energy-level alignment, enabling efficient charge carrier collection in the devices. Meanwhile, CL-MCz synchronously provides satisfied surface wettability and interfacial functionalization, facilitating the formation of high-quality perovskite films with fewer bulk iodine vacancies and suppressed carrier recombination. Significantly, the device with CL-MCz yields a champion efficiency of 23.9% along with an extremely low energy loss down to 0.41 eV, which represents the highest reported efficiency for non-PTAA-based polymer HTMs in inverted PSCs. Furthermore, the corresponding unencapsulated devices exhibit competitive shelf-life stability under various operational stressors up to 2500 h, reflecting high promises of CL-MCz in the scalable PSC application. This work underscores the promising potential of the cross-linking approach in preparing low-cost, stable, and efficient polymer HTMs toward reliable PSCs., (© 2023 Wiley-VCH GmbH.)

Inverted-structure metal halide perovskite solar cells (PSCs) have attractive advantages like low-temperature processability and outstanding device stability. The two-step sequential deposition method shows the benefits of easy fabrication and decent performance repeatability. Nevertheless, it is still challenging to achieve high-performance inverted PSCs with similar or equal power conversion efficiencies (PCEs) compared to the regular-structure counterparts via this deposition method. Here, an improved two-step sequential deposition technique is demonstrated via treating the bottom organic hole-selective layer with the binary modulation system composed of a polyelectrolyte and an ammonium salt. Such improved sequential deposition method leads to the spontaneous refinement of up and buried interfaces for the perovskite films, contributing to high film quality with significantly reduced defect density and better charge transportation. As a result, the optimized PSCs show a large enhancement in the open-circuit voltage by 100 mV and a dramatic lift in the PCE from 18.1% to 23.4%, delivering the current state-of-the-art performances for inverted PSCs. Moreover, good operational and thermal stability is achieved upon the improved inverted PSCs. This innovative strategy helps gain a deeper insight into the perovskite crystal growth and defect modulation in the inverted PSCs based on the two-step sequential deposition method., (© 2022 Wiley-VCH GmbH.)

We found the binding affinities of amide naphthotube to neutral organic molecules in water are not influenced by most of small biomolecules, inorganic salts, and PBS and Tris buffers but are reduced in HEPES buffer through competitive binding. Nevertheless, salts do change the binding affinities of amide naphthotube to charged molecules through a screening effect., (© 2022 Wiley-VCH GmbH.)

Zero-dimensional (0D) hybrid metal halides with perfect host-guest structures are promising candidates to construct circularly polarized luminescence (CPL)-active materials. However, it still remains challenging to obtain 0D chiral metal halides with simultaneously strong CPL and high photoluminescence quantum yield. Here, a new enantiomeric pair of 0D hybrid lead-tin bromides, (RR/SS-C 6 N 2 H 16 ) 2 Pb 0.968 Sn 0.032 Br 6  ⋅ 2H 2 O (R/S-PbSnBr ⋅ H 2 O), is reported. The R/S-PbSnBr ⋅ H 2 O compounds not only show intriguing self-trapped exciton emissions with near-unity quantum yield, but also present intense CPL with a dissymmetry factor g lum of ±3.0×10 -3 . Such CPL activities originate from the asymmetric [SnBr 6 ] 4- luminophores in R/S-PbSnBr ⋅ H 2 O, due to the induced structural chirality by the organic ligands via N-H⋅⋅⋅Br hydrogen bonds. Furthermore, CPL emissions with tunable colors from R/S-PbSnBr ⋅ H 2 O and dehydrated compounds are reversibly observed, which extends their chiroptical applications., (© 2022 Wiley-VCH GmbH.)