Science China Chemistry最新文献

Investigation of luminescent materials with efficient photoluminescence (PL) and mechanoluminescence (ML) is significant for the development of both basic theories and industrial applications for new light sources, pressure sensors, and information security. In this study, we obtain a pair of isomorphic europium(Eu)³⁺-containing coordination polymers (CPs), namely, [Eu(tfpd)₃(phen)]_n (1) and [Eu(tfpd)₃(bipy)]_n (2) (tfpd = 4,4,4-trifluoro-4-pyridyl-1,3-diketonate, phen = 1,10-phenanthroline, bipy = 2,2′-bipyridine), which exhibit novel helical chain-like structures that can be extended to 3D supramolecular networks through moderate interchain interactions. The thermostable CPs simultaneously exhibit strong photoluminescence (PL) emissions with high quantum yields and excellent mechanoluminescence (ML) activity with an unusual anti-thermal quenching effect. Careful analyses of the CP crystal structures and optical performances, coupled with theoretical calculations, demonstrate that the PL emission depends on the asymmetric Eu³⁺ coordination spheres, whereas the ML activity is significantly correlated with molecular packing derived from appropriate interchain H-bonding interactions. As these CPs have highly efficient optical activities, they have promising potential applications in pressure sensing, anti-counterfeiting, and fingerprint recognition technologies.

Despite utilization of state-of-the-art Cu-based catalysts, achieving high selectivity and stability in multicarbon (C₂₊) compounds production through electrocatalytic CO₂ reduction reaction (CO₂RR) remains a critical and challenging objective. Here we employ lattice chlorine-doped Cu₂O nanocubes (Cl_d-Cu₂O NCs) with well-defined {100} facets as a model catalyst to demonstrate that halogen doping can serve as a versatile and effective strategy for modulating surface charge distribution, thereby enhancing asymmetric C–C coupling toward high-selectivity C₂₊ products in CO₂RR. Compared to Cl-free Cu₂O NCs, Cl_d-Cu₂O NCs exhibit a greatly enhanced C₂₊ Faraday efficiency, i.e., ∼85% at −1.1 V (versus the reversible hydrogen electrode). Additionally, the Cl_d-Cu₂O NCs demonstrate significantly enhanced long-term durability, attributed to better preservation of the cubic morphology and more stable Cu^δ+ states. In-situ electrochemical studies reveal that Cl_d-Cu₂O NCs facilitate the formation of the key asymmetric *COH and *OCCOH intermediates, ultimately leading to higher C₂₊ products. Density functional theory (DFT) calculations confirm that the introduced Cl-dopants disrupt the charge balance of the Cu₂O(100) surface, enriching the Cl-adjacent Cu atoms with more electrons compared to those near O atoms. This unbalanced charge distribution significantly reduces the free energy of the rate-determining step for asymmetric C–C coupling from the *CO to *OCCOH on Cl-doped Cu₂O (100) surface, requiring only 1.04 eV, in contrast to 1.50 eV on pristine Cu₂O(100) surface. This study provides valuable insights into the surface charge modulation of Cu₂O catalysts via halogen doping for enhancing asymmetric C–C coupling and C₂₊ production in CO₂RR.

Six-membered and seven-membered carbocycles are prevalent in nature due to their low ring strain and structural stability. In this work, we introduce a novel photocatalytic skeletal editing strategy for Dowd-Beckwith ring expansion acylation, leveraging tetrabutylammonium decatungstate (TBADT) as a hydrogen atom transfer (HAT) photocatalyst. This innovative approach enables the efficient synthesis of a diverse range of six- and seven-membered cyclic ketones under mild conditions, offering key advantages including environmental sustainability, high atom and step economy, good functional group tolerance, and the potential for extensive downstream functionalization. The versatility of this strategy is further demonstrated by its successful application in the post-synthetic modification of complex pharmaceutical intermediates and its scalability via continuous-flow technology, underscoring its broad utility in synthetic chemistry and pharmaceutical development.

Nonionic poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA)-based inverted wide-bandgap perovskite solar cells (PSCs) are pivotal for advancing all-perovskite tandem architectures and indoor photovoltaics, yet their performance is fundamentally constrained by the hydrophobic nature of PTAA. Herein, we demonstrate a dual-interface molecular engineering strategy to synchronously modulate the perovskite-facing upper interface and substrate-contacting buried interface of PTAA using hydrophilic poly(methyl methacrylate) (PMMA) and poly(3-carboxypentyl thiophene) (P3CT-N). The carbonyl (C=O) groups in PMMA and P3CT-N synergistically enhance interfacial wettability, promoting the controlled crystallization of 1.78 eV wide-bandgap perovskites. Additionally, the carbonyl coordination effectively passivates undercoordinated Pb²⁺ defects, improving charge transport dynamics. Meanwhile, vacuum-level shifting induced by the interface dipole of PMMA and P3CT-N optimizes valence-band alignment, facilitating efficient hole extraction. As a result, the modified PTAA-based single-junction PSCs achieve a remarkable power conversion efficiency (PCE) of 19.38% under AM 1.5G illumination, significantly surpassing the 17.06% of pristine PTAA devices. The sandwich polymer structure-based PTAA design further enhances indoor photovoltaic performance, yielding PCEs of 37.43% and 30.09% under 1000 lux and 200 lux LED illumination, respectively. Moreover, in all-perovskite tandem configurations, the modified hole transport layer (HTL) enables a remarkable PCE of 26.87% under AM 1.5G illumination, outperforming control devices (25.38%). This strategy provides a robust pathway toward highly efficient and stable indoor and all-perovskite tandem photovoltaics based on wide-bandgap perovskite.

Hydrogen species participate in the whole process of electrochemical CO₂ reduction, which is traditionally treated as a negative factor from the competitive hydrogen evolution reaction. Here, we illustrate for the first time that the rapid transfer of hydrogen species can significantly promote the deep reduction of CO₂ to ethylene products on copper-based catalysts. We construct a hydrogen transfer channel on Cu₂O nanowires by introducing a conductive copper meso-tetra(4-carboxyphenyl)porphine (Cu-TCPP) layer, where the Cu nodes can adsorb H₂O and the coordinated carboxyl group can adsorb H_ad simultaneously. The hydrogen species from the bulk solution are transferred to the CO₂ reduction step by forming H₃O⁺ with target H₂O and exchanging with the adsorbed H_ad. Density functional theory (DFT) calculations reveal that the channel eventually facilitates the continuous exothermic hydrogenation reaction of the C₂ intermediate towards ethylene production, which accelerates the ethylene generation with the highest faradic efficiency of 78.6% in neutral conditions in H-cells.

Chiral supramolecular polyelectrolyte nanoporous membranes (CSPPMs) are increasingly important owing to their potential applications in sensing, separation technology, and bioengineering. However, developing such membranes remains challenging due to the lack of suitable synthetic approaches. Herein, we introduce a facile and conceptual approach that uses water molecules as dynamic crosslinkers and pore-forming agents to create CSPPMs from single-component chiral poly(ionic liquid)s. The experimental and theoretical calculation results demonstrated that the supramolecular network of CSPPMs was crosslinked by hydrogen (H)-bonding, C–H⋯π, electrostatic, and π-π interactions. During pore architecture formation in the membranes, an intriguing chiral amplification phenomenon was observed. This phenomenon, combined with the unique fluorescence properties and high enantioselectivity of CSPPMs toward chiral guest molecules, enables easy discrimination of enantiomers under UV lamps or even with the naked eye. The knowledge gained from this fundamental study could serve as a springboard for developing multifunctional chiral polyelectrolyte membranes for diverse applications.

Anionic ligands capable of forming covalent bonds with metal centers serve as a powerful tool for precisely modulating the stereoelectronic properties of catalysts. However, the development and application of chiral anionic ligands in transition metal-catalyzed asymmetric synthesis remain underexplored. Here, we report a chiral anionic ProPhenol ligand, which effectively facilitates the nickel-catalyzed asymmetric synthesis of chiral (hetero)aryl and alkenyl sulfinamides under mild reaction conditions. Remarkably, this catalytic system exhibits exceptional efficiency, achieving high yields and stereoselectivity control with only 0.5 mol% catalyst loading in 5 mmol-scale reactions, underscoring its practical synthetic utility. Comprehensive density functional theory (DFT) calculations reveal that the oxygen-boron interaction between the ligand and substrate plays a critical role in facilitating the transmetalation process, while hydrogen-bonding interactions between the ligand and trityl sulfinylamine (TrNSO) significantly enhance enantioselectivity in this transformation.

The separation of benzene (Ben) and cyclohexane (Cy) is of great value in industrial production, but it is extremely difficult due to their similar boiling points and molecular structures. The exploitation of non-porous amorphous materials into adsorbents with high selectivity and adsorption capacity has attracted continuous and extensive research interest considering their excellent accessibility. Herein, we report the synthesis of three metallo-organic cages (MOCs) with high yield and production scale, which are utilized as excellent nonporous amorphous adsorbents for the capture and separation of Ben. Specifically, T-F achieves an ultrahigh selectivity of 199 for the separation of Ben/Cy (1:1, v/v) mixture in a two-component solid-vapor sorption experiment and shows good adsorption capacity of Ben of 109.39 cm³ g⁻¹ at 298 K, thus presenting a remarkable advantage when compared with the reported adsorbents. The in-situ single crystal X-ray diffraction reveals that the adsorbed Ben molecules locate in the extrinsic clefts formed by adjacent MOCs. This study presents a rare yet successful example that utilizes nonporous amorphous MOCs as Ben sorbents with high capacity and selectivity and provides a new route for the development of adsorption materials.