ABSTRACT N‐Methylation of amines is a crucial transformation for synthesizing valuable compounds. However, conventional N‐methylation methods often rely on hazardous reagents. The electroreduction of CO 2 as a sustainable C1 source presents an attractive alternative. Nevertheless, the direct electrochemical activation of CO 2 requires high overpotentials, often leading to a low Faradaic efficiency (FE). This study presents a CO 2 capture‒conversion pathway for the N‐methylation of amines. High concentrations of nucleophilic piperidine preferentially capture CO 2 , enabling spontaneous C─N coupling, as confirmed by 13 C nuclear magnetic resonance spectroscopy. Moreover, N ‐methyl piperidine (NMP) is produced through an electroreduction process. In situ Raman spectroscopy and theoretical calculations reveal the formation of a key piperidinium intermediate and provide insights into its role in subsequent electroreduction. This pathway effectively suppresses side reactions typical of CO 2 electroreduction, achieving a high NMP FE of 71.6% at −0.6 V versus Ag/AgCl. Furthermore, the CO 2 capture‒conversion pathway produces various N‐methylated amines, such as dimethylamine and 1‐methyl ethylenediamine, with excellent FEs, highlighting the generality and advantages of this approach.

Unlike the conventional polymeric boron-phosphide-based (BP) semiconductors, which exhibit limited reactivity, the neutral monomeric BP motif (1) is extremely reactive and nonexistent under ambient conditions. Herein, we depict the ligand-engineering strategies for stabilizing the elusive species 1, initially by employing stereoelectronically tuned donor-based ligands, followed by their successive incorporation into the smallest metallacycles with induced aromaticity, and hence excellent stability. The electron density distribution and chemical bonding of homo- and heterobileptic ligand-stabilized monomers [(L')BP(L)] (2-7) [L', L = singlet carbenes], and the corresponding neutral 3-membered metal(II)dihalide complexes [BP(MX2)] (8-9') and [((L')BP(L))(MX2)] (10-17) [M = Pd/Pt, X = Cl, Br], are investigated by various quantum chemical methods. The remarkable ligand-switched σ and π aromaticity in the unprecedented mixed d- and p-block planar metallacycles is unambiguously confirmed by NICSzz calculations, ELF, AdNDP, GIMIC, and EDDB analyses.

The surface oxygen vacancy defects generated from the abstraction of lattice oxygen atoms of bulk ceria accompanied by the reduction of CeIV to CeIII, are considered to play a pivotal role in photocatalysis. As ideal molecular models of nanoceria, atom-precise cerium-oxo clusters (COCs) hold great promise in determining the accurate CeIII/CeIV ratio and disclosing the underlying catalytic mechanism. However, the number of COCs, especially those mixed-valent COCs with high surface CeIII concentrations, is very limited on account of their formidable synthetic challenges. Herein, we report the first silsesquioxane-protected COC, Ce13, featuring a fluorite-type Ce13O8 core, which is structurally reminiscent of bulk ceria. The cluster exhibits a substantially high CeIII/CeIV ratio with one central CeIV encapsulated by twelve surface-exposed CeIII atoms, serving as a molecular analogue of highly reduced ceria surfaces. This cluster shows strong light-harvesting ability that covers the entire visible range and demonstrates high photocatalytic activity and selectivity for oxidative coupling of various amines, where superoxide radical was involved using O2 as the oxidant at room-temperature under visible light. The surface CeIII sites are proposed to significantly enhance the adsorption and activation of O2. These results highlight the potential of Ce13 as an efficient sustainable photocatalyst for organic transformations.

Nanofibrous architectures, a prominent class of one-dimensional nanomaterials, continue to captivate researchers in the exploration of novel nanofibrous materials and their diverse applications in nanotechnology. Creating crystalline nanofibers with inorganic walls capped by organic ligands is both critical and challenging, requiring precise structural control and consistent internal diameters. Herein, through anion-directed assembly, we demonstrate the controlled creation of semiconducting silver nanofibers with tunable and uniform internal diameters, exemplified by [V3O10@Ag22(iPrS)14(CH3COO)2Cl]n (Ag22-NF), [Cl3@Ag21(iPrS)14(PhCOO)4]n (Ag21-NF), and [Ag6(iPrS)4(PhCOO)2]n (Ag6-NF). Importantly, Ag22-NF encapsulates V3O105- ions within a ∼ 6.52 Å diameter; Ag21-NF contains Cl- and silver ions within a ∼ 5.69 Å diameter; and Ag6-NF is a hollow, template-free nanofiber with a diameter of ∼ 4.57 Å. These nanofibers were further fabricated through mechanical exfoliation of three distinct silver single crystals, preserving their well-ordered structural integrity and alignment with the bulk crystal architecture. As a concept-of-application, the field-effect transistor devices based on Ag6-NF exhibit high ratios of on to off current at ∼ 104-107, demonstrating the outstanding semiconducting performance. This work not only unveils a diverse array of connecting building units that generate nanofibers within three distinct assemblies but also elucidates the profound influence of template size on their optical properties, thereby exemplifying the intricacies of anion-directed design in controlled nanoscale synthesis.

The deliberate construction of well-defined heterostaples within atomically precise metal clusters offers a powerful route to heterometallic systems with unconventional functionalities and promising catalytic potential. However, realizing such precise interface engineering in palladium-based clusters remains highly challenging. Here, we report the first successful synthesis of well-defined Pd5Au2 and Pd5Cu2 architectures featuring heterometallic interfaces by customizing dual-atom site (Au-Au or Cu-Cu) in atomically precise palladium cluster. Their structures were unambiguously determined by single crystal X-ray diffraction (SCXRD) and electrospray ionization mass spectrometry (ESI-MS). Both heterometallic clusters share a similar architecture, comprising a slightly folded Pd5S hexatomic ring encapsulating a central antimony atom from PhSb2- ligand, a M2S3 (M=Au or Cu) staple and four bridging thiolate ligands. Incorporation of the Au-Au or Cu-Cu subunit modulates the geometric and electronic environments of the palladium core to varying extents, leading to markedly distinct two-electron oxygen reduction reaction performances. Notably, Pd5Au2 achieves a nearly 100% H2O2 Faradaic efficiency at 25 mA cm-2 and an exceptional H2O2 production rate of 1366.4 mmol gcat-1 h-1 at 125 mA cm-2. Its efficacy was further demonstrated in practical Fenton-type pollutant degradation. Density functional theory (DFT) calculations, corroborated by operando infrared spectroscopy, reveal that the introduction of an Au-Au dual-atom site induces an electronic redistribution that weakens the *OOH adsorption, thereby facilitating its hydrogenation step. This study represents the first realization of atomically precise palladium-based clusters equipped with heterometallic interfaces, providing new mechanistic insights and design principles for cluster-based catalysts in small-molecule energy conversion.

Environmental nitrogen pollution resulting from various sources (e.g., industrial/municipal wastewater and agricultural runoff) poses a tough global challenge. Traditional approaches for transforming nitrogenous contaminants to inert N2 are often restricted by large operational costs, high energy dependence, and severe reaction bottlenecks. Recently, the discovery of direct mechanobiological activation has inspired a new frontier emerged, highlighting the potential to promote nitrogen conversion via an unprecedented abiotic-biotic synergy enabled by ferroelectric and piezoelectric materials. While previous reviews have focused on either bioelectrochemical nitrogen transformation or piezocatalytic nitrogen conversion, there is no comprehensive discussion that integrates these two domains and elucidates their interfacial coupling mechanisms. This review is aimed to fill this gap by critically examining this synergistic paradigm. We dissect how these materials function dually: they act as abiotic catalysts that form localized electric fields and reactive species, directly activating nitrogen molecules, and simultaneously as biotic stimulators that electronically interface with microbes, enhancing their metabolic denitrification pathways. How this synergy breaks conventional limitations is elaborated. The abiotic pathway can generate favorable microenvironments or intermediates used by the biotic pathway, while microbial activity in turn prevents catalyst fouling. However, practical application requires addressing the critical challenge of energy mismatch with ambient environments. Thus, key emerging strategies are assessed, including photo-mechanical synergy using sunlight as the primary power source while weak mechanical forces restrict charge recombination, and flexoelectric effects that harvest energy from low-frequency non-uniform strains. Harnessing this abiotic-biotic synergy through next-generation concepts can offer a transformative method for sustainable nitrogen remediation.

Mn-oxo clusters,as molecular magnetic materials,were promising candidates for magnetic materials due to their different oxidation states with variable numbers of unpaired electrons and variable geometric arrangements[1].The magneto-structural correlations and the solvent effect on properties in such clusters remain an inchoate area that de-serves to be explored in detail.

Integrating functional ligands into titanium-oxo clusters (TOCs) represents a pivotal strategy for expanding their light-harvesting capabilities and structural diversity. Although various ligand systems have been extensively investigated, the assembly of TOCs using quinoline derivatives-a class of classical photoactive ligands-remains largely underdeveloped. In this work, 2,8-quinolinediol (H2QD) was employed as a versatile ligand to synthesize three novel TOCs, namely [Ti4(mu 2-O)4(QD)4(DMF)4] (Ti4), [Ti5(mu 3-O)2(QD)4(MeO)8] (Ti5), and [Ti7(mu 2-O)(mu 3-O)3(QD)(EtO)18] (Ti7), through a solvent-controlled synthetic strategy. Notably, structural analysis revealed that these clusters exhibit progressively increasing nuclearity and distinct inorganic core topologies. Benefiting from the incorporation of H2QD, all three clusters showed significantly extended light absorption reaching into the visible-light region. Furthermore, these clusters possessed tunable photoelectric properties, with Ti7 exhibiting superior performance compared to Ti4 and Ti5. This work introduces a promising quinoline-based ligand platform for the construction of structurally novel and functionally diverse TOCs.

Hydrogen-bonded organic frameworks (HOFs) have garnered considerable attention as versatile, metal-free porous materials with exceptional potential for enzyme encapsulation and biosensing applications. Despite their inherent biocompatibility and tunable porosity, challenges such as stability under physiological conditions and scalable synthesis remain. In this review, we present a comprehensive overview of recent advances in HOF engineering to enhance enzyme encapsulation efficiency, stabilization, and catalytic activity. This framework integrates molecular design strategies including hydrogen bonding, selective biomolecule recognition, pore size tuning, and co-encapsulation with cofactors to create a protective microenvironment that prolongs enzymatic function under harsh conditions. Cutting-edge HOF-based materials are also highlighted as high-performance platforms for biosensing, integrating optical, electrochemical, and Raman-based methods to achieve ultrasensitive biomolecule and disease marker detection. Furthermore, we discuss the emerging biomedical and therapeutic applications of HOF-based composites, including cell protection, targeted drug delivery, and bioorthogonal catalysis. Key challenges, such as framework stability under physiological conditions, scalability of synthesis, and device integration, are critically evaluated, along with future research directions for clinical translation and industrial application. Collectively, these advances position HOF-based systems as next-generation materials for robust, efficient, and multifunctional biocatalysis and diagnostics.

ConspectusAtomically precise metal nanoclusters (NCs) are a class of nanomaterials composed of a specific number of metal atoms stabilized by well-defined organic ligands. These NCs exhibit molecular-like electronic states and offer exceptional control over their optoelectronic properties. Recent advancements have extended their photoluminescence deep into the near-infrared II (NIR-II) window (950-1700 nm), a spectral region that provides significant advantages for biomedical imaging and photonic applications, including reduced tissue scattering, minimal autofluorescence, and enhanced penetration depth. In comparison to conventional quantum dots and larger plasmonic nanoparticles, atomically precise metal NCs offer unprecedented tunability in terms of emission wavelength, quantum yield, and photostability, facilitated by the modulation of size, composition, and ligand shell chemistry.In this Account, we highlight cutting-edge strategies, including ligand engineering, core-shell engineering, and alloying, which enable fine-tuning of NIR-II photoluminescence in metal NCs. We also explore the photophysical mechanisms underlying NIR-II emission, such as core-ligand charge transfer, metal-centered transitions, and the role of surface electronic states in radiative recombination efficiency. Advanced spectroscopic techniques, such as time-resolved photoluminescence and transient absorption, are discussed for their ability to probe excited-state lifetimes and energy transfer processes that control the emission properties. Finally, we critically address the current limitations in quantum yield enhancement, long-term photostability, and biocompatibility while outlining future directions for developing hybrid materials and multifunctional NC platforms and advancing NIR-II photonic technologies. Our Account aims to offer molecular-level insights and guide the rational design of next-generation atomically precise metal NCs as versatile materials for advanced NIR-II photoluminescence.

Precisely integrating an organometallic compound into atomically defined copper clusters holds great promise for boosting catalytic performance and uncovering detailed structure-activity relationships. Herein, we report the first successful synthesis of atomically precise copper clusters (Cu11-DPPF, DPPF = 1,1-bis(diphenylphosphino)ferrocene) carrying ferrocene units using DPPF and cyclohexanethiol as coligands through a straightforward, scalable, and versatile synthetic strategy, which is also applicable to synthesize its analogous Cu11-DPPM (DPPM = bis(diphenylphosphino)methane) and Cu11-DPPE (DPPE = 1,2-bis(diphenylphosphino)ethane) clusters. All three Cu11 clusters exhibit a similar structural feature like a cloverleaf-like rotational assembly, comprising three fused butterfly-shaped Cu5S7P2 subunits. Among them, Cu11-DPPF exhibits superior catalytic performance in the two-electron oxygen reduction reaction (2e- ORR), achieving H2O2 selectivity exceeding 97.5% within the whole potential range of 0.35 to 0.55 V versus the reversible hydrogen electrode (RHE), fully deserving to be called the optimal 2e- ORR catalyst in the metal cluster community. DFT simulations, in conjunction with multiple characterization techniques such as operando infrared spectroscopy and X-ray absorption fine structure spectroscopy, reveal that the introduction of ferrocene units in Cu11 clusters facilitates favorable electron redistribution, which optimizes the adsorption of OOH* in the rate-determining step, thereby promoting efficient conversion of OOH* to H2O2. The practical efficacy of Cu11-DPPF is further demonstrated in Fenton-like reactions for hydroxyl radical-initiated pollutant degradation via in situ H2O2 generation. This work provides crucial insights into the design of atomically precise ferrocene-functionalized copper cluster hybrid catalysts and deepens our understanding of their structure-activity relationships in 2e- ORR pathways for H2O2 production.

Metal nanoclusters (NCs), as an important branch in the field of nanotechnology, offer significant application potential in catalysis, sensing, materials, and other fields due to their unique physical and chemical properties. In educational contexts, introducing atomically precise nanoclusters helps students gain a deeper understanding of the fundamental principles and application prospects of nanotechnology. Unlike metal nanoparticles (NPs), atomically precise NCs exhibit superior structural precision and controllable properties, serving as ideal model systems for teaching nanomaterials and nanotechnology. This undergraduate experiment course was conducted by ten second-year undergraduate students in group work, which consists of four sessions: a class on the synthesis, purification, and a class on scale-up synthesis of Ag6, followed by a class on the next week covering single-crystal structure determination and a class on optical property measurements, as the growth of the single crystals will take about a week, involving hands-on engagement with cutting-edge scientific research instruments such as single-crystal X-ray diffraction (SCXRD), fluorescence spectroscopy, and mass spectrometry. The course has been well-received by ten upper-division applied chemistry majors, who confirmed its suitability for balancing complexity and engagement. Through this course, students not only synthesize nanoclusters and observe their structural features but also enhance their experimental proficiency, critical thinking, and innovative capabilities, thereby laying a solid foundation for future scientific research.

Developing high-performance dual imaging applications, such as fast neutron and X-ray applications, using a single material presents a very significant challenge across chemistry, material science, physics, and engineering. Integrating both imaging capabilities into a single material for specialized detection applications will simplify device design and significantly reduce overall detection costs. This work represents the first demonstration of a lead-free system designed for high-performance dual imaging applications. It features a multifunctional hybrid copper(I) iodide scintillator, in which hydrogen-rich and luminescent units are synergistically coupled at the molecular level, enabling the simultaneous imaging of fast neutrons and X-rays. The perfect synergy of exciton confinement and thermally activated delayed fluorescence (TADF) effects empowers this material with exceptional dual imaging capabilities. The confined structure formed by heavy-atom modules at the core imparts a high exciton binding energy, suppressing the nonradiative recombination of excitons. The TADF mechanism channels phonons generated by high-energy radiation into the radiative recombination process. Additionally, the lack of self-absorption guarantees efficient photon utilization. Leveraging these properties, the material achieves an impressive X-ray light yield of approximately 42,000 photons/MeV and an exceptional spatial resolution of 25.8 lp/mm for X-ray imaging, surpassing most commercial scintillators available in the X-ray market. Furthermore, the material demonstrates an outstanding spatial resolution of 1.47 lp/mm in fast neutron imaging, representing the best level reported to date for a Pb-free scintillator. This environmentally friendly and high-performance multifunctional scintillator significantly advances next-generation scintillation materials, presenting exciting opportunities for high-precision and dual imaging applications at a low cost.

Silsesquioxanes as versatile organic-inorganic hybrids with terminal siloxyl sites have been utilized to construct diverse metallasilsesquioxane complexes, yet their niche in silver nanoclusters remains largely unexplored. Herein, we report the first silsesquioxane-protected superatomic silver nanocluster, [Ag40(Ph4Si4O8)6(tBuC≡C)8] (Ag40), acquired through an "adaptive multipath synthesis" that circumvents the long-standing limitations imposed by hard and soft acids and bases principles in Ag(I) coordination chemistry. Single-crystal X-ray diffraction analysis reveals a kernel-shell architecture: a face-centered-cubic Ag168+ kernel, encapsulated by a [Ag24(Ph4Si4O8)6] cage and tBuC≡C- ligands. Synthetic methodology studies indicate that the macrocyclic all-cis-T4: Ph4Si4O84- ligands can be accessed via three distinct routes: in situ generation, pre-synthesis, and hierarchical-synthesis, all of which involve the hydrolytic condensation of PhSi(OR)3 (R = Me, Et). Of these, the hierarchical approach addresses the limitations of the other two routes (poor stereochemical control in the in situ route and delayed supersaturation-induced slow crystallization in the pre-synthesis route), improving both the reproducibility and the growth efficiency of the Ag40 crystals. The mass spectrometry analysis not only provides compelling evidence for in situ transformation from cis,cis-T3 to all-cis-T4 ligands but also reveals the assembly pathways for the Ag40 nanocluster either in pre-synthesis or in hierarchical-synthesis, underscoring the dynamic transformation of cyclic oligomeric silsesquioxanes and its critical role in capturing the ultrasmall subvalent silver kernel. Notably, Ag40 exhibits superatomic 1D→1P transition-dominated red phosphorescent emission, persisting in nondegassed solutions. As the highest-nuclearity oligosiloxane-capped metal cluster and first superatomic silver-silsesquioxane species, Ag40 establishes a paradigm for silica-supported superatom synthesis and advances hard-base-protected coinage metal nanoclusters.

The epigenetic silencing or remarkably diminished expression of STING in cancer cells, along with the structural and functional impairment of the endoplasmic reticulum (ER) and Golgi apparatus, represents a unique mechanism of tumor immune escape and poses an important challenge for STING-targeted therapies. Here, we develop a cell membrane-derived nanodisc system (ND-cGAMP-HP; HP, heparin), which is capable of presenting activated STING proteins in their native form by means of cell membrane-directed display and biological self-assembly techniques. It can directly introduce activated STING protein to tumor cells and circumvent the translocation process between the ER and Golgi apparatus, selectively activating the IFN-I signaling pathway without initiating the inflammation-related pathway NF-κB. ND-cGAMP-HP triggers potent cellular immune responses and remodels the tumor immune microenvironment. Moreover, it augments immune memory by promoting the differentiation of TCF1+ stem cell-like T cells. We thus manifest a strategy based on STING therapy that does not depend on the ER and Golgi apparatus pathways to activate the IFN-I pathway, for cancer immunotherapy.

Efficient CO2 capture from hydrocarbon-rich gas mixtures, such as acetylene (C2H2), ethylene (C2H4), and methane (CH4), is crucial for feedstock purification and natural gas upgrading. Ultramicroporous metal-organic frameworks (MOFs) offer promising platforms for such separations, as their narrow pores amplify molecular discrimination and host-guest interactions. Herein, we present a tetrazole-decorated MOF, Cu-btz, synthesized via a green, water-based route and featuring N-donor-rich ultramicropores that preferentially interact with CO2. Gas sorption measurements combined with dynamic breakthrough experiments demonstrate an unusual inverse selectivity, with Cu-btz favoring CO2 over C2H2. Density functional theory (DFT) calculations suggest that this behavior arises from a cooperative host-guest interaction landscape. Long-range electrostatic interactions from the nitrogen-rich pore environment facilitate CO2 adsorption, while additional weak C-H···O contacts further stabilize CO2 within the confined pore space. Remarkably, the framework structure effectively shields the Cu-N coordination bonds from water intrusion, endowing Cu-btz with exceptional hydrolytic stability (2 years in water at room temperature and 30 days in boiling water) and robustness across a broad pH range (pH 3-10). This combination of unusual inverse selectivity and outstanding stability renders Cu-btz a highly promising material for CO2 capture and hydrocarbon stream purification.