Chinese Journal of Chemistry最新文献

Chiral metal-organic clusters (cMOCs) are characterized by diverse chiral origins, tunable luminescence, and multifunctionality. Among them, chiral aluminum oxo clusters (AlOCs) exhibit unique advantages in terms of resource sustainability and environmental friendliness compared to other cluster materials. Nevertheless, the simultaneous achievement of precise enantiomeric control and optical response within AlOCs remains a critical challenge to be addressed in the field. Herein, we achieve precise control over the transition from chirality to circularly polarized luminescence properties in AlOCs by leveraging their highly flexible and modifiable coordination surfaces through a stepwise ligand functionalization strategy. We employed the Al₂ cluster as a platform with programmable surface coordination sites and introduced classical chiral L/D-valine molecules. We successfully constructed four pairs of alcohol-coordinated pure chiral enantiomers (AlOC-189-L/D-MeOH, EtOH, PrOH, and PDO). Absolute helical structures can be identified in the supramolecular architectures of clusters, achieving unambiguous chirality transfer from chiral ligands to chiral clusters and further to absolute helical superstructures. Hierarchical ligand modification, endowed with a top-down design paradigm, offers a rational and feasible route to cluster functionalization. Based on the excellent replaceability of the Al₂ cluster's surface coordination sites, we achieved chiral-luminescent bifunctional coupling by partially substituting the chiral ligands with π-conjugated naphthyl-based luminophores (HNA/HNN), yielding two new classes of enantiomers (AlOC-190-L/D-HNA and AlOC-190-L/D-HNN) exhibiting bright yellow-green photoluminescence (PL). DFT calculations reveal that this is attributed to a ligand-to-ligand charge transfer (LLCT) luminescence mechanism. Notably, AlOC-190-L/D-HNN exhibited promising circularly polarized luminescence (CPL) activity via the synergy between chiral induction from L/D-valine ligands and intermolecular charge transfer of the HNN ligands. This work not only highlights the highly designable coordination chemistry of AlOC—enabling on-demand integration of specific functionalities through modular ligand substitution—but also establishes a novel "ligand editing" paradigm for developing multifunctional chiral optical materials.

The relentless drive toward miniaturization in the semiconductor industry demands photoresists capable of patterning sub-20 nm features for next-generation extreme ultraviolet (EUV) lithography. Metal-oxo clusters, with sub-5 nm molecular dimensions, structural tunability, and high EUV absorption via metal centers, have emerged as promising EUV photoresist candidates. Advancing next-generation photoresist materials necessitates resolving the inherent trade-offs between sensitivity, resolution, and line-edge roughness. In this work, we report a series of halogenated metal-organic clusters based EUVL photoresists, aiming to modulate the sensitivity, resolution, and line-edge roughness. Here, we report the synthesis of halogenated metal-organic clusters as EUVL photoresists, designed to modulate the resolution-line edge roughness-sensitivity trade-off. Sub-20 nm critical dimensions and line edge roughness below 2 nm were achieved with the clusters by EUVL. The results demonstrated that halogen elements influenced the sensitivity of the clusters. To unravel the EUV-driven reaction pathways, we analyzed the chemical transformations in these clusters after exposure using X-ray photoelectron spectroscopy and Fourier-transform infrared spectroscopy. These findings pave the way for the rational design of high-performance EUV photoresists.

The scarcity of critical raw materials in lithium-ion batteries has driven increasing interest in alternative chemistries, such as sodium- based all-solid-state batteries. Among various solid electrolytes, sulfide-based Na₃PS₄ stands out for its high ionic conductivity and excellent formability. However, its poor interfacial compatibility with conventional high-voltage oxide cathodes remains a major limitation. In this study, we report the successful integration of amorphous Na₂MoS₄—a high-capacity, sulfide-compatible cathode—into Na₃PS₄-based all-solid-state sodium batteries. Benefiting from a moderate redox potential window (1.1–2.7 V vs. Na⁺/Na), Na₂MoS₄ exhibits excellent chemical and electrochemical compatibility with Na₃PS₄, as confirmed by structural and spectroscopic analyses. Further investigation reveals that intimate interfacial contact between both electrodes and the solid-state electrolyte is critical for achieving long-term cycling stability. Based on these insights, the optimized Na₁₅Sn₄ | Na₃PS₄ | Na₂MoS₄-Na₃PS₄-carbon nanofiber cell delivers a reversible capacity of ~372 mAh·g^–1 at 0.1 C and retains nearly 100% capacity over 450 cycles at 0.3 C. In situ impedance spectroscopy further confirms the stability of interfacial resistance throughout cycling. This work identifies Na₂MoS₄ as a highly promising sulfide cathode for high-energy, long-life sodium solid-state batteries and provides valuable design principles for future development of sulfide-based electrode-electrolyte interfaces in next-generation energy storage systems.

A bifunctional squaramide-catalyzed asymmetric synthesis of chiral tricyclic chromans featuring three contiguous stereocenters has been successfully developed. This innovative strategy relies on the synergistic activation of 3-aminophenol derivatives and 4-benzylidenepyrrolidine-2,3-diones by the chiral catalyst, enabling an efficient asymmetric oxa-[3+3]-annulation reaction. The protocol exhibits a broad substrate scope with 34 diverse examples, delivering moderate-to-good yields ranging from 64% to 81%, excellent enantioselectivity (up to 99% ee), and tunable diastereoselectivity (dr up to 15 : 1). Notably, halogen substitution plays a pivotal role in dramatically enhancing stereocontrol, further optimizing the diastereoselectivity of the target products. To validate its practical utility, gram-scale synthesis was successfully conducted without compromising yield or stereoselectivity, and subsequent derivatization reactions confirmed the versatility of the obtained chiral tricyclic chromans. This metal-free, mild reaction system not only enriches the synthetic toolbox for constructing complex chroman architectures, but also provides a versatile platform for the asymmetric synthesis of bioactive molecules containing the chiral tricyclic chroman skeleton, highlighting the significance of enantioselectivity and diastereoselectivity in accessing functionalized heterocyclic compounds.

The surface charge properties and local dipole moment of terminal groups have a significant impact on molecular packing and aggregation performance of non-fullerene acceptors (NFAs) for organic solar cells (OSCs). Here, we utilize the interactions between different building blocks within the molecule to regulate the dipole asymmetry of terminal groups by introducing asymmetric inner side chains. Three NFAs, BTA80, BTA81 and BTA82 are designed and synthesized with different substitutions of benzotriazole (BTA)-based inner side chains. The asymmetric introduction of BTA-based inner side chains can modulate the asymmetric surface electrostatic potential and local dipole moments of the terminal groups through the interactions between BTA and the terminal groups, which in turn modifies the molecular orientation and enhances molecular packing. As the result, D18:BTA82-based OSCs achieve the champion power conversion efficiency (PCE) of 17.70% compared to D18:BTA80 and D18:BTA81-based devices with PCE of 16.06% and 16.65%, respectively. Moreover, by introducing the BTA82 as the third component into D18:L8-BO system, the ternary device exhibits a significant improved PCE of 19.60% compared to the device based D18:L8-BO (PCE of 18.73%). This work provides a novel insight into the design of asymmetric NFAs for high performance OSCs.

Herein, a pair of hydrazone-linked covalent organic frameworks (COFs) were constructed with identical main-chain backbone and distinctive side chains (denoted as BTB-COF and BTD-COF), respectively. With H₂PtCl₆ as the co-catalyst precursor, BTD-COF with ethoxy side chains demonstrated superior photocatalytic H₂ production performance yielding 3708 μmol·g⁻¹·h⁻¹ under visible light irradiation, which was 3.0 times higher than that of its analogue BTB-COF with thioether side chains (1236 μmol·g⁻¹·h⁻¹). Comprehensive studies on the composites of platinum nanoparticles (Pt NPs) with COFs after photocatalytic H₂ generation had revealed the impacts of side chains on the photocatalytic process and the anchoring of Pt NPs within COFs. By contrast with the divalent oxidized-state of Pt on BTB-COF, Pt NPs anchored on BTD-COF existed as metallic Pt⁰ with an uniform size of 2.7 nm, agreeing well with the diameter of pore channels. The nature of metallic Pt⁰ NP was greatly beneficial for the surface charge transfer process and had consequently enhanced the photogenerated carrier separation efficiency, which was supported by the density functional theory calculations. This work elucidates the impacts of side chains on the H₂ generation performance of COFs under visible light, which will further spur the structural evolution of functional COFs materials.

The stereoselective reduction of strained molecules and subsequent synthetic transformations provide an efficient strategy to access multi-substituted carbocycles. These carbocycles are important structural skeletons in natural products and bioactive molecules. We report here a Luche-type enantioselective reduction of cyclobutenones and strained-ring fused cyclic imides. This process utilizes the catalysis of Sc–N,N’-dioxide ligand complex and NaBH₄ as reductant. Moreover, the developed methodology is applicable to the strained olefins, which are not tolerated under metal hydride conditions.

Fluoroalkoxylated heterocycles, such as indoles, holds significant importance in pharmaceuticals and biology. Herein, we report a copper-mediated C4–H fluoroalkoxylation reaction of indoles via a transient directing group (TDG) strategy. This reaction exhibits excellent regioselectivity and broad functional group compatibility, offering a new approach for the synthesis of fluoroalkoxylated indoles. The reaction also represents an unprecedented example of 3d-transition metal-catalyzed C─H fluoroalkoxylation via a TDG strategy.

Structurally-modified acenes with a linear fusion of π-extended systems have shown highly attractive properties and promising applications in semiconductor materials, optoelectronic materials and others due to their unique electronic structures. We have accessed a series of anthra/tetra/pentaquinodimethane-supported organoboranes, Mes*B-A, Mes*B-T and Mes*B-P, with highly tunable emissions from blue to red (~680 nm) by controlling the number of fused benzene rings of the [n]acene core (n = 3–5). Interestingly, these redox-switchable quinoid systems have chemically and electrochemically enabled two-electron oxidations, leading to dicationic anthracene, tetracene and pentacene segments (Mes*B-A²⁺, Mes*B-T²⁺ and Mes*B-P²⁺) as evidenced by new absorption bands in the UV−vis−NIR spectra and spectroelectrochemical studies. Meanwhile, all the molecules feature a π-conjugated, overcrowded ethylene structure that allows for a spin-state transition from closed-shell to the open-shell diradicals (Mes*B-A^2•, Mes*B-T^2• and Mes*B-P^2•) under thermal conditions. This can further be confirmed by the variable-temperature (VT) ¹H NMR and electron spin resonance (ESR) spectroscopy. These organoboranes also experienced an emission change in response to fluoride binding with electron-deficient boron centers. Our current work demonstrates not only the synthetic contribution to [n]acene-based luminescent materials, but also showcases multistate transformations for potential applications depending on well-tuned electronic, magnetic, electron transfer and charge transport mechanisms.