The microporous nature of metal-organic frameworks (MOFs) often limits their capacity to incorporate large molecular guests, such as organometallic catalysts. In this work, we demonstrate a defect-engineering strategy for the Zr-based MOF UiO-66 to generate hierarchical pore structures capable of hosting the bulky Lehn-type complex [Re(bpy-4-COOH)(CO)3Cl]. By introducing missing-linker and missing-cluster defects-both during synthesis and through a selective ligand removal (SeLiRe) process-we modulate the framework's pore structure and volume. Using a post-synthetic modification approach, 2,2'-bipyridine-4-carboxylic acid (bpy-4-COOH) is anchored into the MOF structure via solvent-assisted ligand incorporation, followed by complexation with [Re(CO)5Cl]. A comprehensive suite of characterization techniques including TGA, Ar-physisorption, STEM-EDX, solid-state NMR, XAS and other spectroscopic methods confirmed the formation and uniform distribution of the Re-complex within the MOF porosity. Our results show that the introduced defects and the associated creation of mesoporosity are essential for successful incorporation of the large Re-complex, while nearly defect-free UiO-66 cannot be modified with the ligand post-synthetically. The use of the SeLiRe process enables us to gain reasonable control over the amount of the Re-complex inside the MOF and leads to a homogeneous distribution throughout the particles. Photocatalytic CO2RR experiments show CO as the main product with high selectivity when using TEOA as a sacrificial agent. This work demonstrates the potential of engineering hierarchical porosity in MOFs for immobilizing large, catalytically active molecular species in a stable and well-defined environment.
Alkane elimination reactions between stable magnesium and manganese dialkyls, [LnM(CH2tBu)2] (M = Mg, Mn), and an iridium polyhydride species, [Cp*IrH4] (Cp* = C5Me5), provide a variety of heterobimetallic Mg-Ir and Mn-Ir hydride complexes. In several cases, their solid-state molecular structures are shown to be virtually identical despite fundamentally different electronic properties of Mg(II) (2p6) and Mn(II) (3d5). A direct comparison of the paramagnetic Mn with the diamagnetic Mg analog enables a comprehensive characterization based on a combination of analytical techniques (single-crystal X-ray diffraction, IR, and NMR spectroscopies), especially with respect to the hydride ligands, traditionally difficult to identify in open-shell species. Nevertheless, such congruence is not universal: the nuclearity and M:Ir stoichiometry depend on the nature of the Mg and Mn dialkyl precursors, which in turn is determined by the type of coligand L, and on the presence of proton-donating reagents in the reaction mixture, revealing subtle differences between the Mg and Mn systems in certain cases.
Two-center one-electron (2c-1e) σ bond is a unique class of bonding that departs from the century-old shared electron-pair model of covalent bonds. To resolve their bonding features, it is essential to capture the subtle features of electron density localized between the two centers. Here, we have employed X-ray quantum crystallography (QCr)-based models for a quantitative evaluation of this elusive class of bonds across a diverse series of compounds, which apparently exhibit C•C, C•B, B•B, and Cu•M (M = B, Al, Ga) one-electron bonds. The electron density at the bond critical points of these bonds is notably low and comparable to that typically observed for π···π and other noncovalent interactions. In contrast, the bond orders span a wide range, from ~0.6-approximately half of a single bond-to values ~1. Combined bonding analyses and residual electron density maps obtained from QCr models indicate that these interactions are more appropriately described as weak, noncovalent interactions rather than a distinct subclass of covalent bonds.
Microbial cell factory is a powerful biological tool for synthesizing value-added molecules due to its unmatched sustainability and selectivity. However, the inherent catalytic specificity of natural enzymes limits product diversity. Although photobiocatalysis has expanded enzyme catalytic capabilities, challenges such as laborious enzyme purification, incompatibility with in vivo conditions, and complex unnatural substrate synthesis hinder photobiomanufacturing efforts. Herein, we combine a microbial cell factory with a new-to-nature photobiocatalytic transformation via a modular design that combines aerobic fermentation (Module I) and anaerobic photocatalysis (Module II) to achieve de novo biosynthesis of D-homotryptophan. In Module I, we engineer Escherichia coli equipped with a biosynthetic gene cluster to produce indole-3-acetic acid (IAA) via modifying metabolic flux and multi-copy genetic amplification strategies. In Module II, we develop an efficient synergistic photoredox/enzymatic synthesis of D-homotryptophan from L-serine and IAA by a pyridoxal phosphate (PLP)-dependent tryptophan synthase beta-subunit (TrpB) variant. This work synergistically merges emerging photobiocatalytic reactivity with natural biosynthesis, demonstrating a platform with potential for future biomanufacturing of non-natural products.
1-Methylnaphthalene and the products of hydrogenation exhibit a high hydrogen storage capacity (6.6 wt.%), which makes them extremely promising as liquid organic hydrogen carriers. In this work, effective monometallic catalysts, 15Ni/Al2O3, 15Ni/Al2O3-SiO2, and 15Ni/Sib-ox, were synthesized and first investigated for hydrogenation of 1-methylnaphthalene to 1-methyldecalins. The prepared catalysts were characterized using a set of physicochemical analysis methods: SEM-EDX, TEM, XRD, N2 adsorption-desorption, FTIR and UV-vis-DRS. The catalytic activity of the samples in the hydrogenation reaction of 1-methylnaphthalene (100 min, 4 MPa, 240 °C) was studied in comparison to the traditional catalyst of hydrogenation, Ni Raney. The 15%Ni/Sib-ox catalyst showed a 100% conversion and high selectivity of 85.2% with respect to the target product 1-methyldecalins, while in the presence of Ni Raney, a selectivity of 74.3% was achieved with complete conversion of the substrate.
Emerging evidence increasingly suggests a strong correlation linking the human gut microbiome and bone health, particularly in its ability to modulate bone metabolism and the genesis of bone disorders. It is essential to properly understand the mechanisms of the human microbiome to prevent and treat such bone complications. While several therapeutic and analytical techniques have been explored in the past, tissue engineering has recently gained prominence as a strategy that can take advantage of the microbiome's potential. Within this context, microbial exopolysaccharides represent a promising yet largely overlooked source of functional and structural polysaccharides. These natural polymers have significant potential offering meaningful advancements in creating effective materials for bone repair and regeneration. Their potential roles span from enhancing scaffold architecture and mechanical integrity to modulating immune response and promoting osteogenic activity. This review investigates the dynamic interplay between microbiome and bone health through exopolysaccharide-driven tissue engineering. The use of both gut-derived and non-gut microbial EPS in bone tissue engineering has been emphasized. Further EPS driven strategies and their potential for treating bone dysbiosis and contributing to the development of cell-free scaffolds for bone disorders like osteoporosis and osteoarthritis have been discussed.
Multi-resonance thermally activated delayed fluorescence (MR-TADF) emitters exhibit high photoluminescence quantum yields and exceptional color purity, driving significant interest in high-performance organic light-emitting diode (OLED) applications. Current strategies for constructing full-color MR-TADF emitters rely on intricate structural designs to regulate emission wavelengths, yet overlook critical photophysical parameters (such as emission maximum, excited-state lifetime, and so on) and obscure fundamental structure-property relationships, impeding precise control over photophysical behaviours. To address this issue, this study adopts a unique isomeric design strategy to reveal the basic emission properties of MR-TADF molecules. By systematically probing subtle connectivity differences within conserved mono-boron and dual-boron-based multi-resonant skeletons, the chemical bonding pattern dependent emission property was investigated. The critical factors affecting emission wavelength and excited-state lifetime have been uncovered. The detailed theoretical analyses provided a reasonable explanation for these results. This study establishes a molecular design strategy for precise optimization of emission properties, offering deep insights to facilitate the development of high-performance MR-TADF materials. Moreover, the exceptional device performance of compounds v-DABNA-Cz and x-DABNA with high efficiency and satisfactory color purity demonstrates the practicality and significance of the developed method.
Electrochemiluminescence (ECL) is a technique that couples electrochemical control with photon emission, enabling highly sensitive, label-free imaging without an external light source. The microsecond lifetimes and short diffusion lengths of intermediates generated during the reaction confer excellent spatiotemporal resolution, while the absence of phototoxicity promotes biocompatibility. Previously, ECL microscopy has illuminated systems ranging from single cells to multicellular spheroids. Yet, these works relied on luminol-hydrogen peroxide chemistry, which is limited by weak signals and the sacrificial nature of luminol. Here, we introduce tris(2,2'-bipyridyl)ruthenium(II)/tri-n-propylamine ([Ru(bpy)3]2 +/TPrA) chemistry as a powerful alternative for spheroid imaging. Pre-incubation of cellular spheroids within TPrA, followed by interrogation in [Ru(bpy)3]2 + produces markedly sharper spatial resolution and enables continuous imaging for over 3 h, exploiting the recyclability of the luminophore. Furthermore, this strategy reveals the first sustained afterglow chemiluminescence in a biological system, persisting for minutes after the applied potential has ended. Strikingly, we demonstrate that this methodology can elucidate differences in the ECL emission intensity in spheroids from cancerous and non-cancerous cell lines, likely due to differences in TPrA accumulation. These advances establish [Ru(bpy)3]2 +/TPrA-based ECL as a transformative approach for long-term, high-resolution imaging of three-dimensional cellular architectures with application towards cancerous versus non-cancerous tumor model differentiation.
The electrophilic substitution of indoles represents the predominant functionalization strategy. However, due to the electron-rich nature of the indole scaffold, catalytic asymmetric nucleophilic substitution remains markedly underdeveloped-presenting significant synthetic challenges and standing in stark contrast to its well-established electrophilic counterpart. To overcome these challenges, we herein report a visible-light-mediated, chiral Brønsted acid-catalyzed C2-umpolung of 3-azoindoles, enabling their catalytic asymmetric formal nucleophilic C2-substitution with 2-substituted indoles. This strategy provides efficient access to axially chiral 2,3'-bisindoles in good yields with excellent enantioselectivities, thereby overcoming key challenges in both catalytic asymmetric nucleophilic substitution of indoles and the enantioselective construction of axially chiral 5-5 ring systems. This work not only establishes the catalytic asymmetric formal nucleophilic C2-substitution of indoles and an organocatalytic asymmetric synthesis of 2,3'-bisindole atropisomers, but also introduces a photoinduced umpolung strategy to promote nucleophilic substitutions of indoles, significantly expanding the frontiers of chiral indole chemistry and atropisomeric chemistry.
ConspectusOrbital correlation diagrams are central to chemistry. Based on the symmetry compatibility and orbital overlap amplitude, they link the energy-ordered frontier molecular orbitals (MOs) of reactants and products and have long been a powerful and essential tool for understanding chemical interactions (reactions) and molecular properties. The frontier MOs typically include the highest occupied MOs (HOMOs) and the lowest unoccupied MOs (LUMOs), along with a few nearby orbitals of the reactants. However, it is also known that some reactions cannot be well explained with a few frontier MOs. The main drawback of traditional orbital correlation diagrams is that the orbital energies of the reactants shown in the diagram are calculated assuming they are in free, isolated states. But orbital energy levels can be significantly shifted by external fields and the existence of neighboring molecules. In other words, orbital energy levels can be notably reshuffled when we put reactants "physically" (via electrostatic interactions, Pauli repulsion, and van der Waals interactions) together, even without "chemical" interactions (via orbital mixtures or electron transfers).Here, we introduce a novel concept, "in situ" orbital correlation, and demonstrate its applications. This concept is based on our developed block-localized wave function (BLW), which is the simplest variant of ab initio valence bond (VB) theory. The uniqueness of the BLW method lies in its ability to derive orbital energies of a molecule self-consistently in the presence of other species or external fields, as a BLW solution essentially corresponds to a hypothetical diabatic (or resonance) state, a mathematical construct in which all electron transfers between interacting species are "disabled". In such a way, we can correlate orbitals by considering the field (physical) effects from neighboring species even without any orbital (chemical) interactions.This "in situ" orbital correlation concept was first proposed in the study of the activation mechanism of CO by the diboryne compound B2(NHCR)2, where we demonstrated that when CO approaches B2(NHCR)2, there is a HOMO-LUMO swap in B2(NHCR)2 primarily due to the Pauli repulsion from the carbon lone pair of CO, leading to the compatibility of HOMO and HOMO-1 of B2(NHCR)2 with both π* orbitals of CO. Since then, this concept has been adopted in much of our research. For instance, in our most recent study of NCCL- anions (L = N2, CO, CS), which exhibit notable geometric differences, "in situ" orbital correlation diagrams reveal an orbital swap in the fragment NCC- with the approach of the ligand L and subsequently confirm the C(0) theory proposed by the Frenking group. Previously, we explored the "anti-electrostatic" nature of the Al-Mg bond and confirmed that the bond is purely ionic. This contradicts the view from frontier orbitals of Al(I) and Mg compounds, which exhibit a perfect match for a dative covalent bond between them. Now, with the help of the "in situ" orbital correlation diagram, it becomes obvious that the metal-metal bond is a typical ionic bond, because when the Mg compound is brought close, the energy level of the HOMO of Al(I) compound decreases significantly, leading to a reversal of the HOMO-LUMO energy level order and the extension of the HOMO-LUMO band gap and subsequently minimal probability of any electron transfer. We expect that the novel concept of "in situ" orbital correlation will fundamentally enrich our understanding of chemical reactions, electron transfer pathways, and molecular bonding.
Synthesis of bifunctional cytisine-squaramide derivatives bearing a single amino acid moiety has revealed an unexpected and intriguing chemical challenge. During modification of cytisine squaramates with α-amino acids, base-sensitive amido esters readily underwent hydrolysis, forming poorly soluble amido-acid side products that resisted standard purification and initially obscured their identity. Persistent observation of these elusive precipitates prompted a deliberate co-crystallization approach, which unambiguously revealed their supramolecular nature using single-crystal X-ray diffraction. With this insight, optimized purification strategies allowed isolation of analytically pure Cyt-SQ-OH and its derivatives, which were characterized by complementary spectroscopic techniques, X-ray crystallography and computational studies. Furthermore, the DFT-optimized parameters of all compounds were determined, providing additional insight into their structural and electronic properties. This work highlights the interplay between reactivity, solubility, and supramolecular assembly in cytisine-squaramide-amino acid hybrids, providing a robust platform for future exploration of multifunctional conjugates with potential applications in medicinal chemistry, molecular recognition, and materials science.
Metal-organic frameworks with coordinatively unsaturated metal sites (open metal sites) capable of engaging in orbital interactions with π-acidic gases are of interest for enabling ambient-temperature gas separations, such as hydrogen isotope separations. In view of the weakly π-acidic nature of H2, we sought to strengthen π-backbonding-mediated H2 adsorption through pore confinement effects. Toward that end, we synthesized and characterized the ultramicroporous metal-organic framework CuxZn5-xCl4-yHz(bbta)3 (CuIZn-MFU-4; H2bbta = 1H,5H-benzo(1,2-d:4,5-d')bistriazole), featuring π-basic trigonal pyramidal CuI sites that reside within 7 Å of one another at their closest. Gas adsorption measurements reveal an H2 adsorption enthalpy of -38 kJ/mol, exceeding that of the larger-pore analog (CuIZn-MFU-4l; -33 kJ/mol) and representing the strongest H2 adsorption yet achieved in a metal-organic framework. The stronger H2 adsorption in CuIZn-MFU-4 is attributed to a combination of pore confinement effects and the increased σ-accepting nature of the CuI sites caused by a more electron-withdrawing bbta2- linker, as supported by structural, spectroscopic, and computational evidence. With the strongest H2 adsorption, equilibrium isotope effects in CuIZn-MFU-4 lead to a D2/H2 selectivity (as estimated by ideal adsorbed solution theory) of 1.35 even at 298 K, approaching the values reported below 200 K for conventional porous materials.
Shock waves, disturbances that propagate with supersonic velocity in a fluid, are prevalent in nature and across nearly all natural sciences. They find diverse applications in fields such as medicine, aerospace engineering and physical chemistry, where experiments are conducted mostly in macroscopic tubes with an inner diameter ranging from more than 1 mm up to the meter scale. While the theoretical framework for macroscopic shock waves is well-established, the behavior of shock waves in capillaries with diameters in the micrometer range-referred to as "micro-shock waves"-remains largely unexplored. This paper presents novel experimental investigations on the collision of shock waves in micro-capillaries, a fundamental research that has never been done before. These investigations, involving both steady and unsteady drivers, are of significant importance for shock wave physics in general, especially given the limited research on unsteady shock wave collisions. Even more, they play a crucial role in the analysis of micro-shock waves, since they contribute to a more complete characterization of the post-shock region. With the growing interest in microfluidic devices, this research is also important to advance the understanding of supersonic flows at the microscale. Even in the application of high-repetition-rate laser sources, micro-shock wave physics is involved.
Robust methods to access 3,3-disubstituted oxetanes are desired due to the attractive physicochemical properties offered by the polar 4-membered rings and their potential use as replacement groups for carbonyl or gem-dimethyl functionality in medicinal chemistry. The generation of benzylic oxetane carbocations from oxetanols offers considerable potential, particularly in the generation of diaryloxetanes, a structural type that is seldom reported. To date, however, Friedel-Crafts reactions have been limited to oxetanols bearing an electron-rich aromatic group due to the carbocation destabilizing nature of the oxetane. Here, an alternative Fe-catalyzed Friedel-Crafts reaction is described, employing HFIP as a solvent, enabling oxetanyl carbocation formation directly from oxetanols bearing phenyl and other electron-poor arenes. HFIP with its strong hydrogen bond donor (HBD) ability and enhanced Brønsted acidity cooperatively promotes the generation of the carbocations in the presence of the Lewis acid. The oxetane-HFIP adduct was detected, likely formed reversibly as a stabilizing off-cycle intermediate. The developed methodology enabled the concise synthesis of oxetane analogues of Fenofibrate and Tesmilifene, replacing diarylmethane and benzophenone motifs, respectively. Additional mechanistic studies into the fate of these carbocation intermediates provide insights into the reaction mechanism.
The unprecedented mixed-valent metal-organic framework (MOF) [CuI4CuIIIBr5(Et-dtc)2]·CH2Cl2 (CuBrEt-3D; Et-dtc- = diethyldithiocarbamate), which facilitates solvent desorption, was characterized using single-crystal X-ray diffraction. CuBrEt-3D forms a three-dimensional framework featuring a planar CuIII center coordinated by diethyldithiocarbamate ligands, bridged by CuIBr units. This mixed-valent characteristic was confirmed through solid-state adsorption spectra, revealing a broad absorption extending to 2500 nm, attributed to intervalence charge transfer from CuI to CuIII. Remarkably, this compound exhibits significant air stability despite its mixed-valent nature. SQUID measurements verified its diamagnetic properties. CuBrEt-3D incorporates dichloromethane as a crystallization solvent within its pores, yet the solvent can be removed under mild conditions while maintaining porosity. Impedance spectroscopy demonstrated semiconducting behavior, and band-structure calculations clarified the carrier-transport pathways. CuBrEt-3D was employed as a cathode material for lithium-ion batteries, delivering capacities comparable to those of commonly used LiCoO2.
The article deals with the study of stress corrosion cracking (SCC) of X70 steel using corrosion-mechanical testing that simulates the operating conditions of underground pipelines. The tests were carried out under cyclic four-point bending at stresses close to the yield point, in electrolytes with various hydrogen charging capacities. The following model environments were used: NS4 solution and citrate buffer (pH 5.5). Hydrogen charging was controlled by the addition of thiourea and by varying the potential. It was shown that microcracks initiated at corrosion defects (pits) and then emerged at the surface to form narrow cracks. The incubation period depends on the environment: under corrosive conditions it is approximately two times shorter than in the air. The size and nature of stress concentrators play a significant role: natural pits (~hundreds of μm) lead to crack formation within 24-28 days, whereas artificial holes (0.6-1 mm) lead to crack formation within 5-7 days. The effect of hydrogen was established: the acceleration is insignificant under moderate hydrogen charging, whereas the incubation period decreases sharply at high hydrogen charging. Critical hydrogen concentrations where its effect becomes significant were determined. Methods for inhibiting stress corrosion cracking by means of organosilicon films (vinyl- and aminosilanes, as well as their mixtures with inhibitors-benzotriazole and amines) were considered. The most effective composition is vinylsilane + benzotriazole: the time to crack initiation increases from 5 to 36 days, and the crack growth rate decreases.
Non-steroidal anti-inflammatory drugs (NSAIDs) are used globally for their pain-relieving and fever-reducing properties. However, excessive intake of NSAIDs can have harmful effects on multiple body systems, including the cardiovascular, gastrointestinal, hepatic, renal, and nervous systems. The anti-inflammatory activity of 34 derivatives of 1-aryl-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline was investigated in vivo. A relationship between the activity of the compounds and the nature of their substituents, as well as their positional and mutual arrangement in the C ring (1-Ar-), was established. In silico modeling of these 1-aryl-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline derivatives' interaction with the COX-2 (PDB ID: 1PXX) active site revealed that the nitro-derivatives exhibited the highest stability owing to their superior capacity for electrostatic and hydrogen bond formation compared to brominated compounds. These data on the effects of the substituents -NH2, -OH, and -OCH3 in ring C (1-Ar-) of 1-aryl-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinolines on anti-inflammatory activity promote the search for new, highly effective derivatives within this series.
Friction slows down moving objects at both macroscopic and microscopic scales1. At the electronic level, quantum friction describes direct transfer of momentum between a liquid and the electrons of a solid2. Owing to its microscopic nature, this phenomenon remains experimentally challenging to capture3. Here we show that near-infrared fluorescent single-walled carbon nanotubes (SWCNTs) exhibit light-induced quantum friction in water. It is measured by observing an excitation-power-dependent linear decrease of around 50% in the diffusion constants of functionalized SWCNTs in aqueous solution. This effect disappears when excitons are localized, as in the case of SWCNTs with quantum defects. We further show that the chemical manipulation of exciton concentration by molecules that increase or decrease SWCNT fluorescence also modulates the diffusion constant by up to a factor of 2. Optical pump terahertz (THz) probe spectroscopy shows an instantaneous response (around 30 cm-1) that we assign to direct exciton-water coupling in the range of water Debye modes. It is followed by an increasing (>100 ps) response in the range of intermolecular translational modes of the hydrogen bond network of water (>100 cm-1), resembling heating. Classical molecular dynamics simulations further support a mechanism in which the fluctuating dipole moments of excitons create frictional forces. These findings establish light-induced quantum friction between excitons in SWCNTs and water and show that electronic excitations can be used to control nanoscale motion and fluid properties.
Saccharomyces cerevisiae is a keystone host for biomanufacturing, yet its metabolic engineering is often complicated by the crosstalk between heterologous pathways and native metabolism. In particular, allocating and balancing the universal reducing equivalents nicotinamide adenine dinucleotide (phosphate) (NAD(P)H) typically requires laborious genetic modifications. To address this challenge, we established an orthogonal redox cofactor infrastructure in S. cerevisiae based on nicotinamide mononucleotide (NMN(H)), which is decoupled from the host's NAD(P)H-based metabolism because NMN(H)-dependent pathway networks comprise only a small number of user-defined reactions, their optimization is substantially simplified. First, by rewiring glycolysis to eliminate NAD(P)H generation from glucose, we repurposed glucose as a dedicated electron source for NMNH reducing power. We then demonstrated that NMN(H) selectively drives the reduction of citral to citronellal, both unstable aldehydes, while suppressing the rapid over-reduction to alcohols observed with native cofactors without identifying or disrupting the numerous endogenous alcohol dehydrogenases in resting S. cerevisiae cells. Finally, we engineer S. cerevisiae to accumulate an intracellular NMN+ pool of ∼2.9 mM, comparable to NAD+ intracellular levels, enabling the first self-sustained, new-to-nature redox cofactor system in eukaryotic organism. This work establishes NMN(H) as a functional third nicotinamide-based redox cofactor in yeast and provides a generalizable eukaryotic platform for orthogonal redox biocatalysis.
Lithium sulfide (Li2S) is pivotal for high-energy-density lithium-sulfur (Li─S) batteries due to its high theoretical capacity, abundant sulfur resources, and compatibility with anode-free architectures. However, its application is hindered by its intrinsically insulating nature and sluggish redox kinetics. Furthermore, traditional 1,3-dioxolane/1,2-dimethoxyethane electrolytes cannot withstand high voltages and pose safety hazards due to low flash points. Herein, we propose a synergistic strategy by introducing diisopropyl dithiocarbonate disulfide (DIP) as a multifunctional redox mediator into a high-flash-point, high-voltage-tolerant tetraethylene glycol dimethyl ether electrolyte system. DIP directly converts Li2S to lithium polysulfides, decreasing the activation voltage of the first charge to 2.48 from 3.18 V. Simultaneously, DIP facilitates the formation of an organosulfur-rich solid electrolyte interface on the lithium surface, effectively suppressing lithium dendrite formation and growth. Crucially, this system enables stable cycling in anode-free Cu||Li2S batteries for 160 cycles at 0.3 mAh cm-2. Standard Li||Li2S cells also demonstrate superior durability, achieving an extremely low per-cycle decay rate of 0.037% at 1C. Moreover, this strategy holds promise for other metal-sulfur systems, such as Na─S, K─S, Ca─S, Mg─S, and Zn─S batteries, providing a feasible path for safe, next-generation energy storage.