Jing Chen

Traditional hyperhalogen design relies heavily on homoleptic coordination between a metal center and superhalogen ligands, a constraint that fundamentally limits structural diversity in this field. Here, we report a new class of heteroleptic hyperhalogens, [Ag(BO2)(B2O4)]−, [Ag2(BO2)(B2O4)]−, and [Ag2(BO2)(B3O6)]−, which were synthesized in the gas phase and characterized by time-of-flight (TOF) mass spectrometry and quantum chemical calculations. Experimental results show that precise control over the spectral conditions enables the selective synthesis of these clusters. Theoretical calculations demonstrate that the heteroleptic design endows the clusters with exceptional hyperhalogen properties. Electronic structure analysis further reveals a positive correlation between hyperhalogen behavior and the d-orbital contribution from the Ag atoms to the highest occupied molecular orbital (HOMO). This discovery suggests that synergistic interactions between different superhalogen moieties could have broad applicability in synthetic design, offering new perspectives on the coordination chemistry of superatomic clusters and opening a transformative avenue for hyperhalogen research.

While considerable progress has been made in synthesizing ligand‐free all‐metal clusters (LFAMCs) for Groups 14 and 15 within the Zintl phase, achieving stable condensed‐phase analogues for electron‐deficient Group 13 metals remains a significant and unresolved challenge. Herein, we overcome this challenge through a jellium‐guided charge‐engineering strategy that transcends classical Zintl principles, such as the Wade–Mingos and octet rules. By leveraging structure‐directing cations to tune lattice charge, we stabilize a series of ligand‐free super‐chalcogens, BeM ₁₂ (M = Al, Ga, and In), achieving the jellium‐predicted 40‐electron closed‐shell configuration exclusively via ionic interactions. The resulting superatomic CdI ₂ ‐type superlattice, BeM ₁₂ [Y(2,2,2‐crypt)] ₂ (Y = Na, K, Rb, and Cs), exhibits exceptional stability, linearly tunable bandgaps, strong visible‐light absorption, a pressure‐dependent optoelectronic response, and a record‐low exfoliation energy that facilitates straightforward 2D fabrication. Crucially, this superlattice inherits the energetically and spatially separated frontier orbital character of its parent cluster, manifesting electronic behavior unprecedented in conventional ionic materials. A jellium‐based shell‐closing transition (38 → 40 electrons) underpins the assembly, thereby extending the established framework of Zintl‐phase electronic theory. This work establishes a general design principle for stabilizing highly reactive LFAMCs and opens a promising avenue for developing quantum‐confined functional materials.

Cyclo[13]carbon (C₁₃) is inherently antiaromatic and unstable, with an open-shell triplet ground state. Here we show, via first-principles calculations, that encapsulating an alkaline earth atom (M = Ca, Sr, and Ba) within the ring transforms C₁₃ into a closed-shell MC₁₃ complex with significantly enhanced stability. The bonding is predominantly ionic, with the metal atom donating its two valence s-electrons individually to the in-plane and out-of-plane π-systems of the carbon ring. This electron transfer simultaneously achieves two stabilizing effects. It grants the metal center a closed-shell noble-gas-like electronic configuration while providing two additional π-electrons that confer dual aromatic character on the carbon ring. This dual stabilization mechanism, arising from both the closed-shell metal center and the aromatic carbon ring, converts an inherently unstable antiaromatic molecule into a robust aromatic system. Furthermore, MC₁₃ exhibits exceptional nonlinear optical responsiveness under external electric fields, offering a design strategy for field-controllable nonlinear optical materials.

The rational design of superatomic architectures mimicking carbon’s versatility remains a fundamental challenge yet holds promising potential for programmable quantum materials and functional devices. Herein, an octet-rule-derived open-shell ONa₆ superatom, a carbon analogue with a perfectly matching electronic configuration, was designed to form methane-like supramolecules (Na₄@ONa₆ and Br₄@ONa₆) through directional SP³ superhybrid bonding. This enables a bottom-up assembly of 15 cluster-based carbon-like architectures, including metallic diamond and graphite analogues with ultralow work functions, alongside thermally stable perovskite semiconductors featuring linearly tunable band gaps. These supercarbons replicate elemental carbon’s electronic signature while transcending natural allotropes, serving as quantum building blocks for atomically precise 2D lattices and 3D frameworks. Demonstrating programmable functionality from electrocatalysis to robust visible-light seawater splitting photocatalysts, our approach systematically maps structural evolution from atomic clusters to functional materials. These findings may unlock an expanded design space for carbon-transcending functional materials and chemically integrated quantum devices, offering unprecedented opportunities in superatomic chemistry for designing advanced functional materials through the engineering of atomic clusters.

Surface-enhanced Raman spectroscopy (SERS) encounters difficulties in complex sample analysis due to the matrix interference caused by competitive adsorption on SERS substrates. To address this limitation, this work proposes an online-integrated paper centrifugation and SERS (PC-SERS) approach, using a circular paper disk coated with silver nanoparticles (P-AgNPs) as a separation medium and a SERS substrate. The device's functionality is enabled by the differential migration behavior of substances on the P-AgNPs disk through rotation. Upon sample loading at the disk center, centrifugal force drives radial outward diffusion of analytes, solvent, and interferents. The enhanced diffusivity of solvent molecules relative to target analytes on P-AgNPs facilitates more expeditious adsorption of the analytes onto the substrate surface, resulting in higher SERS responses in a short time. Compared with conventional SERS analysis, the PC-SERS enhances signal intensity by 14-fold within a 20 min analysis. Mechanistic studies reveal that target analytes and interferents exhibit distinct interaction forces with the P-AgNPs, causing them to deposit at separated positions on the substrate during outward diffusion, thereby forming characteristic detection zones. PC-SERS effectively resists competitive adsorption, achieving a detection limit of 1 μg·L^-1 for sulfonamide in the presence of strong interferents, which is 2 orders of magnitude lower than static SERS analysis. These enhanced capabilities enable reliable detection of trace sulfonamide antibiotics in complex matrices such as regenerated water (recovery of 84.12-105.27%) and vegetable extracts. Given the rapid analysis and portable operation requirements, PC-SERS is suggested to have strong potential for on-site environmental monitoring applications.

A solid-phase microextraction-SERS (SPME-SERS) analysis system was enhanced by the synergistic integration of azo reaction and electroextraction (Azo/EEx/SPME-SERS) to directly determine aromatic amines in serum and urine. Azo reactions selectively converted aromatic amines (e.g., aniline) into positively charged derivatives, which were selectively absorbed onto a rough silver SERS substrate via charge-selective electroextraction (- 0.2 V), excluding anionic interferents. Electroextraction-accelerated mass transfer and real-time SERS detection enabled rapid preconcentration and spectral acquisition under 3 min. The azo reaction increased the Raman scattering cross-section of aniline, and electroextraction reduced the distance of azo aniline to the SERS hot spots. This enabled low detection limits (aniline, 0.005 µg·mL⁻¹). The Azo/EEx/SPME-SERS method achieved dual-dimensional interference exclusion through chemical derivatization (azo reaction) and physical charge-selective electroextraction, granting aromatic amines competitive adsorption advantage over serum metabolites at SERS hotspots. This synergy allows for the direct detemination of aniline in urine/serum with only 5–10 fold dilutions. It avoids the need for tedious pretreatments, while maintaining recoveries of 92–107%, accuracy of 97.33% (urine) and 94.89% (serum), and method detection limits of 0.05 µg·mL⁻¹ (urine) and 0.5 µg·mL⁻¹ (serum). Graphical Abstract

Aromaticity is one of the most classical concepts in the field of modern chemistry and has been employed to explain and design substances with special stability. Although the knowledge about Hückel's and Baird's rules has been well established, the understanding of Möbius aromaticity remains extremely limited. In this letter, by employing density functional theory (DFT) calculations, we demonstrated that the four-membered VIB transition metal (TM) carbide clusters possess a highly stable open-shell planar tetrameric structure and exhibit double Möbius aromaticity, which was evidenced by analyzing multiple aromaticity criteria, including the electronic, magnetic, and energetic indicators. Each cluster was characterized by four delocalized π electrons and four delocalized σ electrons, forming a novel class exhibiting double Möbius aromaticity. Intriguingly, the unexpected stability of these open-shell clusters was suggested to arise from the hybridization of d-p atomic orbitals, as revealed by analysis of the composition of delocalized orbitals. Our findings highlight the significance of hybridization between the d orbitals of transition metals and the p orbitals of main group elements in the creation of dual Möbius aromatic species, which offers new avenues for the design of single-molecule magnetic inorganic materials.