Hybrid lead halide perovskites have emerged as versatile candidates for advanced optoelectronic applications. However, precise control over their phase interconversion remains challenging. Here, we report two structurally distinct 2D perovskites, S-[BPEA]2PbI4 and rac-[BPEA]2PbI4, featuring near Dion-Jacobson (nDJ) and near Ruddlesden-Popper (nRP) stacking configurations induced by stereospecific organic cations. Under mild hydrostatic pressure, both compounds exhibit significant photoluminescence enhancement (1.97 times at 0.38 GPa, 1.09 times at 0.22 GPa) and tunable emission energies. Notably, S-[BPEA]2PbI4 undergoes a nDJ-to-nRP phase transition, while rac-[BPEA]2PbI4 evolves toward an ideal RP phase, driven by supramolecular interaction modulation and octahedral distortion. In addition, structural analyses, including Hirshfeld surface mapping, deformation potential modeling, and in situ high-pressure PXRD, quantitatively correlate lattice response with emission behavior. Moreover, both materials exhibit reversible mechanochromic luminescence, underscoring their mechanical robustness and optical responsiveness. These findings establish a supramolecular engineering framework for controlling phase structure and light emission in 2D hybrid perovskites via pressure stimuli, enabling their future use in optoelectronic systems.

Photocatalytic coproduction of hydrogen peroxide and high-value organic chemicals presents a highly promising and sustainable pathway for solar energy utilization. Yet, developing bifunctional photocatalysts via a facile and tunable synthetic strategy remains a formidable challenge. Herein, we report a dimensionality-conversion strategy that disassembles conventional two-dimensional metal-covalent organic frameworks (2D MCOFs) into one-dimensional (1D) metallopolymers engineered with directional electron-transfer capability. Incorporation of single-atom Ce sites bearing unpaired f-electrons enables precise modulation of the electronic structure along the polymer backbone, dramatically enhancing photocatalytic performance for the coupled H2O2 photosynthesis and oxidative coupling of benzylamine (BA). The optimized Ce/COP-3 achieves a high H2O2 photosynthesis rate of 3132 & micro;mol g(-1) h(-1) (8.2% apparent quantum yield at 465 nm) and delivers 99% conversion and selectivity for high value-added intermediate N-benzylbenzaldimine (BBAD) in BA oxidative coupling. When integrated as a thin film in a continuous-flow photoreactor, Ce/COP-3 sustains a stable H2O2 production rate of similar to 3000 & micro;mol g(-1) h(-1) over 30 h of operation. This outstanding activity and durability are attributed to the tailored electronic configuration of Ce f-orbitals and an extended exciton diffusion length of up to 6.03 nm. This work provides critical insights into the rational design of bifunctional 1D metallopolymer photocatalysts for next-generation solar driven chemical synthesis.

Copper complexes hold a promise for electroluminescent applications, owing to their dual emissive feature based on the moderate spin-orbital coupling effect of Cu+ ion for controllable singlet-triplet conversion. However, efficient red dual emission from copper complexes remains an important challenge, because emission wavelengths and thermally activated delayed fluorescence (TADF)/phosphorescence (PH) ratios are simultaneously correlated to electronic effects. Herein, fluorine atoms with suitable electron-withdrawing inductive effect were introduced into a typical tridentate phosphine ligand coordinated CuI skeleton, namely, TTPPCuI, to reduce the lowest unoccupied molecular orbital (LUMO) energy levels, giving rise to narrowed energy gaps between the highest occupied molecular orbital and LUMO, corresponding to emission wavelengths red shifted from 574 to 603 nm. Fluorine atoms simultaneously enhance metal-ligand charge transfer, therefore adjusting positive and reverse intersystem crossing for dual emission balance, leading to TADF/PH ratios changing from 56/44 over 75/25 to 83/17. The devices based on these fluorinated CuI complexes realized efficient red electroluminescence with the maximum wavelength and external quantum efficiency beyond 600 nm and 20%, respectively. These results demonstrate that, based on electronic effects from functional groups, ligand engineering is a feasible way for comprehensively manipulating excited-state characteristics of dual-emissive copper complexes.

ABSTRACT Achieving single‐product selectivity in photocatalytic CO 2 reduction remains an enormous challenge. Although modulating a catalyst's nanoconfined environment can mitigate the co‐production of CO and CH 4 in CO 2 reduction, the contribution of nanoconfined architecture to interfacial built‐in electric field (BIEF) regulation for solid‐gas CO 2 conversion has received limited attention. Herein, CsPbBr 3 quantum dots (QDs) are grown in situ within the ordered porosity of boron‐doped mesoporous TiO 2 (BMT) for CO 2 photoreduction under simulated solar irradiation. The composite CsPbBr 3 @BMT delivers a CO production rate of 226 µmol g −1 h −1 with essentially 100% (99.9%) selectivity in a solid‐gas system, outperforming state‐of‐the‐art CsPbBr 3 ‐based photocatalysts under comparable conditions. The new CsPbBr 3 @BMT architecture integrates pore‐level stabilization of QDs, with the nanocage framework isolating and stabilizing the QDs, as evidenced by in situ XPS and TEM. The combination of boron doping and nanoconfinement is shown by theoretical calculations to enhance the BIEF between the QDs and BMT, leading to improved charge separation and suppressed hydrogen evolution. In addition, calculations reveal that nanoconfinement stabilizes the COOH intermediate in CO 2 photoreduction while weakening CO adsorption, directing the system toward CO formation and release. These results highlight nanoconfinement as an effective strategy for selective, efficient solar‐driven CO 2 ‐to‐CO conversion.

The development of durable, high-performance anode catalysts remains a central challenge for proton exchange membrane (PEM) water electrolysis, particularly under conditions of reduced iridium loading and aggressive anodic operation. Ti-supported IrO₂ catalysts represent a promising strategy to improve catalyst utilization and durability; however, the coupled relationships between microstructure, electrochemical performance, and degradation processes remain insufficiently understood. Here, we systematically examine the structure-performance-durability relationships of Ti-supported IrO₂ anode catalysts by combining advanced multiscale structural characterization with electrochemical diagnostics and quantitative image and data analysis. Critical microstructural descriptors include pore architecture and size distribution, IrO₂ agglomerate morphology, Ti support spatial distribution and local density, Ir-Ti interfacial contact characteristics, Ir-ionomer interfacial coverage, ionomer network connectivity, and phase crystallinity. These features are resolved using complementary SEM, TEM, STEM/EDS, and XRD techniques, enabling both qualitative visualization and quantitative, data-driven extraction of structural metrics. Electrochemical behavior is evaluated through polarization measurements, electrochemical impedance spectroscopy (EIS), distribution of relaxation time (DRT) analysis, and steady-state testing, allowing direct attribution of kinetic, transport, and resistive losses to specific microstructural features. In particular, pore architecture and agglomerate morphology are correlated with mass-transport limitations and high-current-density performance; Ti support distribution and Ir-Ti interfacial contact are linked to electronic conductivity and catalyst utilization; ionomer coverage and network connectivity are associated with proton-transport resistance and interfacial charge-transfer kinetics; and phase crystallinity is connected to oxygen evolution reaction (OER) activity and stability. By integrating electrochemical parameters with quantitative microstructural descriptors derived from image and data analysis, this work establishes actionable design rules for optimizing Ti-supported IrO₂ anodes. These insights provide a framework for rational catalyst-layer engineering that simultaneously enhances performance, reduces precious-metal usage, and improves long-term durability in PEM water electrolyzers.

Achieving single-product selectivity in photocatalytic CO2 reduction remains an enormous challenge. Although modulating a catalyst's nanoconfined environment can mitigate the co-production of CO and CH4 in CO2 reduction, the contribution of nanoconfined architecture to interfacial built-in electric field (BIEF) regulation for solid-gas CO2 conversion has received limited attention. Herein, CsPbBr3 quantum dots (QDs) are grown in situ within the ordered porosity of boron-doped mesoporous TiO2 (BMT) for CO2 photoreduction under simulated solar irradiation. The composite CsPbBr3@BMT delivers a CO production rate of 226 µmol g-1 h-1 with essentially 100% (99.9%) selectivity in a solid-gas system, outperforming state-of-the-art CsPbBr3-based photocatalysts under comparable conditions. The new CsPbBr3@BMT architecture integrates pore-level stabilization of QDs, with the nanocage framework isolating and stabilizing the QDs, as evidenced by in situ XPS and TEM. The combination of boron doping and nanoconfinement is shown by theoretical calculations to enhance the BIEF between the QDs and BMT, leading to improved charge separation and suppressed hydrogen evolution. In addition, calculations reveal that nanoconfinement stabilizes the COOH intermediate in CO2 photoreduction while weakening CO adsorption, directing the system toward CO formation and release. These results highlight nanoconfinement as an effective strategy for selective, efficient solar-driven CO2-to-CO conversion.

Emissions of sulfur-containing pollutants from fuel oil combustion are facing progressively stricter controls amid rising environmental demands. Herein, a highly efficient metal‒organic framework catalyst RMOF-Zr has been successfully synthesized, which the framework is functionalized with N-hydroxyphthalimide (NHPI) moieties. When hydrogen peroxide (H2O2) was used as the oxidant, the as-fabricated RMOF-Zr achieved efficient deep desulfurization within 60 min in the oxidative desulfurization (ODS) process and exhibited excellent recyclability. Based on the experimental results, a possible synergistic catalytic mechanism is proposed. The Zr clusters promote the decomposition of H2O2 to generate reactive oxygen species (ROS). These ROS then trigger the activation of NHPI, which further facilitates the ODS process through synergistic catalysis. This work provides new ideas for designing strong synergistic catalytic effects between catalytic sites and metal clusters in the same framework.

Cu/Pd-cocatalyzed cascade asymmetric alkene boration and Z-retentive allylic substitution reactions are described. Taking advantage of palladium catalysts that well tune the rates of both the π-σ-π isomerization process of the π-allyl-palladium species and nucleophilic substitution, either Z-retentive or Z-to-E allylic substitution reactions can be achieved, with alkyl copper nucleophiles generated in situ via Cu-catalyzed alkene boration. Chiral Z- and E-olefins containing an organoboronate functional group are afforded under Cu/Pd relay catalysis from the same starting materials. Both reactions proceed with high yields (up to 95%), excellent Z/E ratios (up to >19:1), and good enantioselectivity (up to 94% ee).

A Pt-Co catalyst supported on ZIF-8-derived porous carbon (Pt-Co/Z-HP) with strong metal-support interaction (SMSI) was developed for efficient room-temperature formaldehyde (HCHO) oxidation. The catalyst exhibited highly dispersed Pt nanoparticles, abundant surface hydroxyl groups, and a defect-rich nitrogen-doped carbon matrix. These features promote Pt stabilization, oxygen activation, and intermediate conversion, achieving nearly 100% HCHO removal and CO2 selectivity under ambient conditions. Density functional theory (DFT) calculations further revealed that plasma-induced -OH species regulate the surface coverage of active hydroxyls, maintaining a balance between O2 activation and HCHO adsorption. Moreover, comparative models of isolated Co and Pt clusters (Conp-Ptnp-NC) and Pt-Co alloy clusters (CoPtnp-NC) demonstrate that the alloy structure achieves lower reaction barriers for both O2 dissociation and HCHO oxidation via synergistic dual-site cooperation. These findings highlight that appropriate -OH coverage and Pt-Co electronic synergy are critical for enhancing catalytic performance. This work provides a low-energy approach for designing advanced volatile organic compounds (VOCs) oxidation catalysts via tailored SMSI.

Introducing both locally excited and charge transfer (CT) featured single-molecule long-lived excited states in energy transfer can optimize room-temperature phosphorescence (RTP) at molecular level, but this requires accurate energetic modulation and sequential populations of these states. Herein, we utilize intermolecular interactions between donors (D) and/or acceptors (A), namely, the external electronic effect, to modulate intramolecular CT in a linear system named POMPDPAC containing N-(3-methylphenyl)-9,9-diphenylacridine (MPDPAC) donor and diphenylphosphine oxide (DPPO) acceptor. Theoretical simulation and time-resolved photophysical results show that intermolecular D-A or D-D/A-A interactions give rise to two stabilized ππ* and CT-featured triplet states on a single POMPDPAC molecule in its two different dimers, whose incorporation in the RTP process establishes a step-by-step energy transfer. As a result, compared to its Br or diphenylphosphine (DPP)-modified congeners only with ππ* featured triplet states, RTP quantum yield and lifetime of POMPDPAC powder are improved as high as ∼3 and 5-11 folds, respectively, accompanied by 77% RTP ratio in photoluminescence and typical photochromic properties. This work demonstrates not only the possibility of coexistence of multiple stabilized single-molecule triplet states in organic solids, but also the feasibility of developing multifunctional "RTP+" materials.

Optical waveguide materials serve as fundamental building blocks for integrated photonic systems, which have a wide range of applications in optical communications. Micro-crystals as active optical waveguide materials can provide the technical foundation for achieving small-sized and high-density integrated devices. However, how to achieve planar anisotropy and multi-directional optical waveguides in 2D crystals remains challenging. Herein, Au2Ag2(R/S-POT)4 (POT: 4-phenyloxazolidine-2-thione) with blue circularly polarized luminescence (CPL) emission at 455 nm and photoluminescent quantum yield (PLQY) up to 93.5% is designed. Parallelogram Au2Ag2 core induces orientation arrangement of peripheral ligands and further promotes regular 2D stacking, enabling crystals to form high crystallinity and smooth surfaces. Crucially, the chiral structure promotes highly anisotropic molecular packing in the formed 2D crystal, which leads to the induction of anisotropy in the ordered packing direction by the parallel orientation transition dipole moment (TDM), with a linear polarization ratio of 0.61. Meanwhile, 2D crystals exhibit direction-dependent waveguide characteristics with optical loss coefficient (OLC) of 0.01 (D1), 0.0178 (D2), and 0.0161 dB mu m -1 (D3), respectively. This work not only establishes a feasible strategy for anisotropic waveguides of 2D clusters but also introduces 2D micro-structures that hold promising potential for applications in information encryption.

Abstract The development of red cluster light-emitting devices (CLED) lags far behind blue and green congeners with respect to efficiencies, since multiple excited states of red cluster molecules are involved in non-radiation during electroluminescence. Herein, we accurately optimize excited states of a red bipyramidal [PXZDPPQ] 2 Cu 4 I 4 , whose ligand integrates conjugation-extended 2-diphenylphosphineylquinoline (DPPQ) and strong electron-donating phenoxazine (PXZ), giving rise to desired excited state locations of the outer intraligand charge transfer ( n LCT)-featured first singlet (S 1 ) and triplet (T 1 ) excited states and the inner high-lying metal-ligand charge transfer ( n MLCT) states. Its outer and highly radiative n LCT states are spatially and energetically advantageous in carrier capture and exciton confinement; meanwhile, its inner and high-lying n MLCT states are protected from collisional quenching, and support cross transitions between n LCT states to realize exactly balanced dual emissions with a ratio of 51/49. [PXZDPPQ] 2 Cu 4 I 4 achieves eightfold increased photoluminescence quantum yield of 93.6%, tenfold increased external quantum efficiency reaching 43.7% as a new record for all kinds of planar red light-emitting devices, and 20% improved exciton utilization efficiency in comparison to the congener with the reverse excited state location. These results demonstrate the unique merit of cluster materials in exciton engineering and their potential for next-generation full-color displays.

By employing a non-metal doping strategy, we systematically achieve the stabilization and synergistic modulation of both surface defects and spin polarization within a wide-bandgap semiconductor. This platform is crucial for advancing key applications in both environmental remediation and energy conversion. Optimized photocatalytic activity in TiO2 is achieved by tailoring its electronic structure through a template-assisted route, where boron acids act simultaneously as dopants and mesopore-directing agents. Mechanistically, advanced techniques including PAS, EXAFS, OCPD and DFT calculations reveal spin polarization in TiO2 arises when interstitial boron pairs with nearby oxygen vacancies form B-Ov complexes that stabilize vacancy-derived defect states and, via local dipoles and distortion of TiO6 octahedra, break spin degeneracy near the Fermi level (Ef), thereby suppressing spin-allowed recombination and enhancing photocatalytic charge utilization. Notably, employing boron also enables precise control of hierarchical porosity and surface area in metal oxides. The resulting TiO2-x bearing spin-polarized B-Ov complexes delivers CO from CO2 at 24 mu mol h-1 g-1 with high selectivity and degrades tetracycline under visible light within 2 h (k = 0.016 min-1), which are 6- and 16-fold faster than pristine TiO2 and TiO2-based photocatalysts reported under similar conditions. This work presents a significant advance in the methodology for constructing next-generation free-standing photocatalysts.

A series of [Cu(bipy) (P boolean AND P)]BF4 complexes, where P boolean AND P is a sterically hindered P,P-bis(mesityl)-substituted 1,5,3,7-diazadiphosphacyclooctane, were obtained. The structure of complexes was fully characterized by different analytical and spectroscopic techniques (NMR spectroscopy, mass-spectrometry, single-crystal and powder X-ray analysis). The X-ray analysis reveals a distorted tetrahedral geometry of around the copper(I) ion. The electronic excited states were investigated by UV/Vis and luminescence spectroscopy and identified using density functional theory (DFT) and time-dependent density functional theory (TDDFT) methods. All complexes exhibit a multiband emission in deep-blue and red regions of the visible spectrum. A comprehensive analysis of photophysical data allowed us to assign a high-lying (Sn) singlet excited state responsible for a deep-blue emission band, while the S1 singlet and T1 triplet excited states - for red emission bands. A small energy difference between the S1 and T1 emissive states ensures the thermally activated delayed fluorescence (TADF) performance of the complexes. The complexes retain their luminescence properties when doped into the PMMA matrix. Heteroleptic [Cu(bipy) (P boolean AND P)]BF4 complexes can be considered as promising luminophores for further OLED development, while their polymer composites can be applied in temperature sensing devices.

Erbium-doped waveguide amplifier (EDWA) is important for long-haul optical communication, whose gains by population inversion require high Er3+ densities and limited concentration quenching. Herein, we demonstrate the first example of erbium clusters named Er5(DBM)10 and Er9(acac)16 for high-gain EDWAs, in virtue of their multi-erbium cores for “spatial energy confinement”. The single-crystal packing diagrams and photophysical investigations indicate that highly concentrated Er3+ ions in the clusters and enlarged intermolecular distances simultaneously confine and share excited-state energies in the cores via Er-Er energy migration, and suppress collisional quenching, leading to increased emission intensities and elongated lifetimes. As consequence, under 377 nm LED pumping, compared to its mononuclear congener Er(acac)3, Er9(acac)16 markedly increases output optical intensity of its evanescent-field waveguides by 464

Lanthanide nanocrystals offer unique advantages for electroluminescence (EL) applications, including narrow-band emission, high colour purity and compositionally tunable output1-4. However, their insulating nature poses a challenge for carrier transport and injection, impeding their application in electrically driven optoelectronic devices5. Here we demonstrate efficient EL from insulating lanthanide fluoride nanocrystals (4 nm; NaGdF4:X; X = Tb3+, Eu3+ or Nd3+) coated with a series of functionalized 2-(diphenylphosphoryl)benzoic acids (ArPPOA). These ligands, featuring donor-phosphine oxide acceptor hybrids with carboxyl and P=O coordination sites, effectively sensitize the luminescence of lanthanide nanocrystals by modulating the intraligand charge transfer characteristics. Ultrafast spectroscopic investigations reveal that strong coupling between ArPPOA and lanthanide nanocrystals facilitates intersystem crossing (ISC; <1 ns) and highly efficient triplet energy transfer to nanocrystals (up to 96.7%). Through careful control of dopant composition and concentration in nanocrystals, we also achieve wide-ranging multicolour EL without altering the device architecture, reaching an external quantum efficiency exceeding 5.9% for Tb3+. This ligand-functionalized nanocrystal platform provides a modular strategy for exciton control in insulating nanocrystal systems, offering a pathway for spectrally precise electroluminescent materials.

To achieve efficient DMDS degradation, we systematically designed a peroxodisulfate-intercalated CoFe layered double hydroxide (CoFe-LDH-PDS) with a PDS-embedded layered structure as the core component. By modulating the interlayer architecture through PDS insertion, the catalyst demonstrates three critical functions: (1) expanded interlayer spacing (0.753→0.760 nm) facilitating rapid DMDS diffusion, (2) in-situ generation of sulfate radicals (·SO₄⁻) via PDS activation, and (3) stabilization of Co²⁺/Co³ ⁺/Fe²⁺/Fe³ ⁺ redox cycles for sustained electron transfer. When activated by dielectric barrier discharge (DBD) plasma, which acted as an excitation source, the PDS-intercalated system achieved > 85 % DMDS degradation efficiency, outperforming conventional LDH by 39 %. EPR and DFT analyses revealed PDS intercalation enhances interfacial electron transfer through dual pathways: charge transfer (0.43-0.55 e-) and d-orbital optimization (Fe d-electron center shift from -3.04 eV to -2.63 eV). Crucially, plasma excitation synergizes with PDS-derived radicals through energy transfer, creating an efficient degradation cycle. This work establishes an atomic-level design framework for intercalation-enhanced catalysts in energy-assisted environmental remediation.

Herein, we report a chiral Brønsted-acid-catalyzed dearomatization of quinolines. The reaction proceeds via dearomative hydride transfer and subsequent enantioselective semipinacol rearrangement. The key to this reaction sequence is to guide the imine intermediate to a rearrangement pathway other than over-reduction. Utilizing a bulky chiral imidodiphosphorimidate catalyst guarantees the desired reactivity. A series of chiral spiro tetrahydroquinoline products is afforded in good yields (up to 93%) and enantioselectivity (up to 93% ee). Detailed mechanistic insights are obtained based on DFT calculations.