In this study, we successfully designed and synthesized a pyridine-modified tris(2,4,6-trichlorophenyl)methyl radical (PyTTM). PyTTM exhibited notably rapid single-crystal formation in acetone. Single-crystal X-ray analysis revealed that molecular planarity and multidimensional intermolecular non-covalent interactions were key factors driving its fast crystallization. Compared to TTM, PyTTM showed significantly enhanced photostability. The introduction of the pyridine group endowed PyTTM with reversible acid–base responsiveness and excellent cycling stability. Furthermore, the triangular radical ligand was able to self-assemble with temed-Pd(NO₃)₂ into a one-dimensional macrocyclic chain. This work offers a promising design strategy for novel luminescent radicals that combine high stability, rapid crystallization, and acid–base stimulus responsiveness.

An electrochemically mediated selective C(sp³)–S/C(sp²)–S bond cleavage of heteroaryl alkyl sulfides has been developed. This conversion features transition-metal-, oxidant- and catalyst-free conditions, involving dealkylation or desulfuration transformation with operational simplicity and good functional group tolerance. Besides, scale-up experiments and single-path continuous-flow electrosynthesis were used to demonstrate the potential of this transformation in practical organic synthesis.

The skeletal remodeling of nitro-biphenyl indoles has been achieved via the cleavage of C₂–N₁ bond of and redistribution of the C₂ atom. A diverse range of phenanthridines and phenanthridine N-oxides were switchably synthesized through fine-tuning the amount of HCl and reaction atmosphere. The scale-up synthesis and late-stage modification of the resulting products expand the application potential of this methodology. Furthermore, DFT calculations indicate that the ring-opening of indole necessitates the assistance of EtOH. This work establishes an attractive platform for the remodeling and conversion of N-heterocyclic frameworks.

Fe−N−C materials, boasting exceptional catalytic activity, stand out as ideal candidates for replacing platinum-group metals in catalyzing the oxygen reduction reaction (ORR). However, their stability is challenged by the attack of oxidative radicals generated from the incomplete reduction of H₂O₂. Inspired by the antioxidant mechanisms of natural organisms, Se dopants were introduced with antioxidant properties into the Fe−N−C materials to serve as effective H₂O₂ scavengers. Experimental results reveal that the Se-doped samples are capable of swiftly catalyzing the H₂O₂ disproportion decomposition, markedly diminishing the H₂O₂ yield and consequently decreasing the generation of reactive oxygen species (ROS). Furthermore, the incorporation of Se significantly enhances the corrosion resistance of the carbon substrate. Capitalizing on the synergistic impact detailed above, the series of Se-modified Fe−N−C catalysts all exhibit significantly superior stability compared to their undoped counterparts in acidic media. Our work provides a proactive defense strategy for enhancing the durability of the Fe−N−C catalysts and forges a novel route for the development of highly stable non-noble metal ORR catalysts.

Helically twisted molecular architectures are critical motifs in both biology and synthetic supramolecular chemistry, with unique functional properties derived from their chiral geometries. Although lemniscular (figure-eight) macrocycles with a noncontact crossover point have attracted increasing interest, their metallosupramolecular analogs remain underexplored, largely because of synthetic challenges that hinder precise control. Herein, we report a coordination-driven strategy for the controlled construction of lemniscular metallacycles by exploiting the linear coordination geometry of Ag^I and Au^I complexes containing N-heterocyclic carbene (NHC) ligands. The key to this approach is the design of a bis-NHC imidazolium ligand containing helicene moieties, which promotes homochiral helicene dimerization and suppresses noncrossover macrocycle formation. Ag^I and Au^I–NHC lemniscular architectures were synthesized via this method, and the Au^I complex was validated through multiple synthetic pathways. The generated structures were characterized via electrospray ionization mass spectrometry, ultraviolet–visible absorption and fluorescence emission spectroscopy, X-ray crystallography, and density functional theory calculations, confirming the formation of the target metallacycles. Notably, this work addresses the long-standing scarcity of metallosupramolecular lemniscular systems, increases the structural diversity of macrocycles, and establishes a platform for the systematic investigation of the emergent functionalities of these complexes.

We present here a straightforward protocol for the enantioselective synthesis of axially chiral tetrasubstituted allenes enabled by chiral phosphoric acid (CPA)-catalyzed 1,8-addition of indolizines to propargylic alcohols. This strategy achieves enantioselective and regioselective C1-functionalization of indolizines under mild reaction conditions with low catalyst loading, broad functional group tolerance (35 examples), and excellent enantioselectivities (up to 96% ee). Moreover, the scale-up reaction and late-stage C3-functionalizations demonstrated its potential applications. DFT calculations were carried out to clarify the reaction mechanism and the origin of enantio- and regioselective control.

The design of cross-scale morphological structures has emerged as a fundamental strategy to tune electromagnetic response behaviors. However, challenges remain in precisely regulating the morphological structures of absorbers. Herein, the VN@hierarchical porous carbon/cobalt@carbon nanotubes composites were synthesized through sol-gel self-propagation method. By adjusting the Co element proportion, the evolution of the carbon nanotube on the surface of microstructure can be regulated. The sample with a molar ratio of 3 : 7 (Co : V) attained a reflection loss value < −20 dB across a wide frequency range (3.68–16.48 GHz) at varying thicknesses. The excellent performance is imputed to the synergistic effect of hierarchical nano/micro-structure in the samples. Furthermore, the coating resulting from the macroscopic metamaterial design achieved an ultra-wide effective absorption bandwidth of 12.55 GHz with a minimum reflection loss of −62.37 dB at an equivalent thickness of 2.77 mm, and the maximum radar cross-section reduction value reached 40.74 dB·m². This work not only provided a novel strategy for developing electromagnetic wave absorbing composites with multi-band response capabilities, but also emphasized the potential of morphological structural engineering for designing ultra-wideband absorbers in practical applications.

The development of carbon dioxide (CO₂) capture and utilization is of vital importance. However, previous photocatalytic reduction reactions for converting CO₂ into chemicals (e.g., CO, HCOOH, CH₄, or CH₃OH) rely heavily on sacrificial reagents. Herein, we disclose a visible light photoredox-catalyzed 1,2-difunctionalization of terminal alkynes by using CO₂ as an ideal quenching reagent and the xanthene dye Rhodamine 6G (Rh-6G) as a photocatalyst (PC) via consecutive photoinduced electron transfer (ConPET) process. The newly developed CO₂-triggered reaction provides a highly regio- and stereo-selective approach to diverse functionalized (E)-α-vinylsulfones with simultaneously efficient conversion of CO₂ into oxalate. The practicality of this protocol is demonstrated by late-stage modification of alkynes derived from biologically active natural products or drugs. Preliminary mechanistic studies suggest that the homocoupling of CO₂ radical anion results in the formation of oxalate.

Structural transformation of metal−organic frameworks (MOFs) involving significant rearrangement of coordination bonds represents a powerful strategy to construct novel structures with distinct functionalities. While such transformations are typically driven by solvent, ion, or heat stimuli, the potential of functional macrocycles to trigger framework reconstruction remains unexplored. Herein, we disclose the first macrocycle-mediated dimensional reduction of a MOF, where the introduction of cucurbit[6]uril (CB[6]) induces 3D-to-2D structural transformation through a dissolution-recrystallization mechanism. This transformation involves the breakage and reformation of coordination bonds and the incorporation of CB[6] within the framework through multiple outer-surface interactions. The resultant 2D layered framework (CB[6]@Zn-TCA-L) demonstrates enhanced stability in aqueous solutions, attributed to the ordered arrangement of CB[6] macrocycles with the encapsulation of Me₂NH₂⁺ cations in their cavities. Furthermore, the combination of its 2D layered structure featuring accessible Lewis acidic metal sites and abundant active sites on the CB[6] surface enables CB[6]@Zn-TCA-L to function as a highly efficient catalyst for the cycloaddition of CO₂ with various epoxides under mild conditions.

A novel visible-light-driven protocol has been established for the direct difunctionalization of unactivated alkenes using arylhydrazines and H-phosphine oxides as dual-function reagents. Through visible-light photocatalysis, phosphonyl radicals are generated as key intermediates, which undergo a cascade process involving radical addition, single-electron oxidation, and dehydration coupling to achieve the in-situ construction of C–P and C=N–N bonds. The method demonstrates broad substrate compatibility with excellent functional group tolerance, delivering β-phosphinoyl hydrazones in moderate to good yields. Notably, several synthesized compounds exhibit potent anti-proliferative activity against HepG2 cells. Mechanistic investigations through radical trapping experiments and kinetic studies confirm a radical chain pathway, with photocatalysis crucially mediating the initial radical generation and subsequent electron transfer processes.

Polyether materials, derived from the ring-opening polymerization (ROP) of epoxides, are widely used in biomedicine and functional materials. However, due to the steric hindrance of the high-freedom substituents, monosubstituted epoxides are difficult to activate and exhibit the characteristics of being difficult to polymerize. In addition, traditional anionic ring-opening polymerization (AROP) usually has functional group tolerance problems. As such, it is of great significance to develop efficient catalytic systems to achieve the polymerization of monosubstituted epoxides. In this work, a series of tetranuclear aluminum complexes [Al(R¹)₃(ONO)AlR²]₂ (ONO = N-methyl aminodiethylate ligand) featuring the neutral AlR₃ molecules coordinated to oxygen atoms on ligand framework have been synthesized and characterized. These complexes can efficiently catalyze cyclohexene oxide (CHO) polymerization through the synergistic effect between aluminum metals, and the iso-butyl substituted tetra-aluminum complex [Al(ⁱBu)₃(ONO)Al(ⁱBu)]₂ shows the highest reactivity (TOF of 3792 h^–1) at 30 °C. Notably, this tetranuclear catalyst demonstrates exceptional catalytic activity in the polymerization of monosubstituted epoxide substrates. Mechanistic investigations elucidate the distinct roles of the aluminum centers in the synergistic catalytic systems for the first time: the neutral AlR₃ moiety serves as the initiator for ROP, whereas the Al–R group functions as a Lewis acidic activator that facilitates epoxide monomer activation. This study provides important guidance for the controlled synthesis of polyether architectures from monosubstituted epoxide precursors.

A variety of metal coordination modes that may provide carbon-carbon bond cleavage pathways in benzene and benzenoid hydrocarbons are summarized in a rubric. Some of these are evident in recently published work, and others represent challenges for future research. The first category includes thermolyses and ring opening metathesis polymerization of iridium η⁴ adducts, aluminum(I) additions that first yield η² 1,2- or 1,4 adducts, intramolecular C=C metatheses that involve initial 1,2 Mo=C additions, multimetallic activation via dititanium η³ binding modes, and a one-off lutetium mediated process that defies simple classification. However, few of these transformations are currently catalytic. The interpretation of most has been aided by DFT calculations, and related lines of investigation are briefly treated.

Known for high sensitivity and significant signal-to-noise ratio, chemiluminescence (CL), a phenomenon dependent on chemiexcitation via chemical reaction, has gained much attention in the field of in vitro detection, biosensing, and in vivo imaging over the past few years. Albeit its fulminant development, bottlenecks, such as poor stability, limited structural tunability, low emission intensity, and uncontrollable reaction rates restrict biological applications and further practical translation. Therefore, researchers have been dedicated to improving CL performance for broader and meaningful programs. This review first provides a concise outline of the basic concepts of CL, luminescence mechanisms, and development history, then summarizes key optimization strategies focused on three main areas for improving imaging performance: extending the emission wavelength, enhancing luminescent properties, and improving synthetic feasibility, followed by ending with a discussion of emerging opportunities and future directions in chemiluminescence research.

Polysubstituted indoles, integral to pharmaceuticals and bioactive natural products, highlight the strategic importance of indole multifunctionalization in drug discovery. This review comprehensively summarizes the recent advances in multifunctionalization reactions of indoles, focusing on the development of three key methodologies: cyclization, di-, and trifunctionalization, while simultaneously providing an organized framework for understanding catalytic system development, regioselectivity control mechanisms, and cascade reaction design paradigms in this field. Specifically, the content delves into various catalytic systems, encompassing transition metal, metal-free, organic, and photo/electrochemical approaches for indole multifunctionalization. Particular emphasis is placed on elucidating regio- and chemo-selectivity patterns across various indole sites, along with considerations of orthogonal functional group compatibility. By addressing the absence of comprehensive reviews in this field, this review aims to serve as a valuable reference for advancing indole chemistry, while inspiring new breakthroughs and innovations that will drive the field to new heights.