The circular economy has emerged as a pivotal and irreversible future direction for the sustainable development of the global plastics industry, aiming to alleviate the severe environmental pollution and resource waste caused by traditional non-degradable plastics. Chemical recycling to monomers (CRM) converts waste polymers directly back to monomers, offering a highly promising approach to enabling a circular plastics economy. Poly(1,3-dioxolane) (PDXL) is an ideal thermoplastic for CRM owing to its excellent chemical recoverability, outstanding thermal resistance, and robust mechanical properties, making it a competitive alternative to commercial petroleum-based polyolefin plastics. In this work, high-efficiency ring-opening polymerization of 1,3-dioxolane (DXL) to prepare PDXL was successfully achieved in high activity using perfluorinated triphenylborane (B(C₆F₅)₃), while the unfluorinated analogue triphenylborane (BPh₃) is inert to the polymerization of DXL under identical reaction conditions. The as-prepared PDXL features a high number-average molecular weight of 178 kDa at a monomer-to-catalyst ratio ([DXL]/[B(C₆F₅)₃]) of 700 : 1, excellent thermal stability with 5% thermal decomposition temperature of 356 °C, and superior tensile strength (σ_B = 30 MPa), which far exceeds that of conventional commercial polyethylene materials. Significantly, the key active species involved in the polymerization process was isolated for the first time via equimolar reaction of B(C₆F₅)₃ with DXL, and thoroughly characterized by nuclear magnetic resonance (NMR) spectroscopy and single-crystal X-ray diffraction analysis. Based on the crystal structure of active species, the detailed mechanism of the ring-opening polymerization of DXL has been proposed and confirmed through density functional theory (DFT) simulations. Furthermore, chemical recyclability of PDXL was accomplished using phosphotungstic acid (PTA) as a catalyst, yielding high-purity DXL monomer with high conversion, even in the presence of pigment additives or mixed plastic waste. PTA can be recovered and reused repeatedly for the depolymerization process. This work offers a feasible and efficient strategy for metal-free catalyst-mediated preparation of chemically recyclable polymers, promoting the advancement of circular plastics.

Mechanochromic luminescent (MCL) compounds, possessing emission-color-change feature under mechanical stimulus, are attracting much attention due to their potential applications in optical recording, chemical sensor and information encryption. However, most of the current reported MCL compounds are donor-π-acceptor (D-π-A) structure, which are unfavorable to achieve spatial conformational regulation towards property modification compared with those possessing spatial D-A stacking structure. Herein, we propose a synergistic strategy, namely simultaneously regulating molecular polarity and steric hindrance, to construct a series of D-A type compounds for MCL property modification. Through adopting 9-phenylfluorene as the molecular skeleton to interrupt π-conjugation and using N-ethylcarbazole as electron donor together with 4,6-diphenyl-1,3,5-triazine as acceptor to regulate molecular polarity, we successfully unlock the MCL property in D-A type target compounds. Notably, after 9-phenylfluorene is introduced into N-ethylcarbazole position for increasing the steric hindrance, more obvious MCL behavior with a large emission red-shift of 38 nm is achieved. Moreover, the target 9-phenylfluorene derivatives are evaluated towards potential application in information encryption. It is expected that our study provides an inspiring strategy to develop new MCL materials for multifunctional application.

Self-assembled interlayers are widely used to improve electrode/semiconductor contacts in optoelectronic devices and their properties can be fine-tuned through rational molecular design. In molecular semiconductors and interfacial modifiers, substituent position is known to profoundly influence molecular conformation, packing motif, and dipole orientation. Here, we adopt this strategy and introduce different methoxy substituent positions in self-assembled interlayers. Two positional isomers, o-DMPCz and m-DMPCz, are synthesized and employed as hole-transporting interlayers (HTLs). Their impact on interfacial energetics and charge transport is explored through density functional theory, molecular dynamics simulations, together with surface-potential, electrochemical, and conductive-probe measurements. These investigations show that the ortho-methoxy isomer (o-DMPCz) exhibits a larger dipole moment, stronger adsorption, denser packing, and higher interfacial conductivity, leading to more efficient hole extraction and reduced interfacial recombination. In PM6:BTP-eC9 OSCs, the o-DMPCz interlayer yields a power conversion efficiency of 19.53%, outperforming m-DMPCz (14.48%) and PEDOT:PSS (18.45%), due to simultaneous gains in short-circuit current and fill factor. Similar efficiency improvements in PM6:Y6 and PM6:L8-BO systems highlight the generality of this positional-isomer strategy. This study reveals the key role of substitution sites in self-assembled interlayers and provides a design framework for high-performance interfacial materials in OSCs and other emerging optoelectronic devices.

The Aldol reaction of α-branched aldehydes with α-carbonyl aldehydes is a key organic synthetic transformation, which can directly construct high-value chiral 1,4-dicarbonyl compounds bearing quaternary carbon centers. However, few catalysts can efficiently mediate this asymmetric Aldol reaction. Thus, the development of highly efficient catalysts for such reactions represents a crucial strategy to address the aforementioned challenges. Herein, we report a series of novel C₂-symmetric chiral bifunctional primary amine catalysts that can efficiently promote this transformation. These catalysts employ 1,3-propanediamine as the linker and Tle-DPro as the catalytic moiety, and can be readily prepared via concise and efficient amide condensation steps. Under mild reaction conditions, this catalytic system efficiently catalyzes the asymmetric Aldol reaction of α-branched aldehydes with α-carbonyl aldehydes, affording a series of chiral 1,4-dicarbonyl products with excellent yields (up to 99%) and enantioselectivities (up to 99%). Notably, the C₂-symmetric bifunctional primary amine catalysts developed in this work can efficiently accommodate both α-branched and linear aldehydes. In contrast, classic organic secondary amine catalysts exhibit unsatisfactory performance, which unambiguously demonstrates the prominent superiority of this catalytic system for these transformations. Scale-up experiments demonstrate that this method exhibits promising industrial application potential. Furthermore, the obtained product ent-3a can be further converted into various high-value compounds, including α,β-unsaturated esters, chiral pyridazinones, (R)-pantolactone, and D-calcium pantothenate. In addition, HR-MS, ¹H NMR analyses, and kinetic studies (initial rate measurements) were conducted to preliminarily elucidate the reaction mechanism and reveal the catalyst structure–performance relationship, which provides a valuable reference for the further design and development of chiral primary amine catalysts.

The defluorination-enabled functionalization not only provides an effective strategy to mitigate fluoride pollution, but also opens new avenues for constructing molecular diversity. Although numerous methods for C–F bond activation have been developed, their applications are typically confined to single defluorination-monofunctionalization processes. Traditional approaches to achieve 1,1-dual modification rely on multistep reaction sequences or precious-metal catalytic systems, which suffer from inefficiency, high cost, and significant environmental burden. In this study, we report the first electroreductive strategy for one-pot 1,1-deuterocarboxylation of C(sp³)–F bonds using cost-effective deuterium oxide (D₂O) as the deuterium source and carbon dioxide (CO₂) as a sustainable C1 feedstock. This method demonstrates broad substrate compatibility with difluoro-/trifluoroalkylarenes and enables late-stage drug functionalization without pre-activation. Mechanistic studies confirmed that the reaction proceeds via a sequential pathway: the substrate undergoes initial reduction at the cathode, reacts with CO₂, and then undergoes reduction by deuterium protonation in the presence of D₂O, ultimately leading to the formation of the final product.

Herein, we report a cooperative photoredox/cobalt catalytic system for the direct synthesis of trisubstituted Z-homoallylic alcohols via the reductive coupling of allenes with formaldehyde (formalin solution or paraformaldehyde). This method delivers products in high yield with excellent regioselectivity and stereoselectivity. The reaction is mild, water compatible, scalable, and exhibits broad functional group tolerance. The reaction proceeds under exceptionally mild conditions at room temperature, features low catalyst loadings (as low as 0.1 mol% for the photocatalyst and 2 mol% for the cobalt catalyst), and exhibits excellent functional group tolerance. A wide range of aryl, heteroaryl, and alkyl-substituted allenes undergo smooth conversion, delivering the desired Z-olefin products in moderate to good yields with complete γ-regioselectivity (>19 : 1 rr) and high to excellent Z-stereoselectivity (up to >19 : 1 Z/E). The synthetic utility of this method is demonstrated through a gram-scale synthesis (72% yield, 2.2 g) and diverse subsequent transformations of the homoallylic alcohol product, including hydrogenation, epoxidation, Mitsunobu reaction, and Appel bromination, all of which proceed without erosion of the Z-alkene geometry. Mechanistic studies support an oxidative cyclometalation pathway.

Click chemistry has boasted remarkable connectivity in molecule synthesis. The fluorosulfonyl group is not only an important structural motif in bioactive molecules, but also serves as a useful SuFExable group in the next-generation click chemistry, sulfur(VI) fluoride exchange (SuFEx) reactions. In this study, we successfully developed a facile synthetic approach to β-ethynyl sulfonyl fluorides, by leveraging the synergistic catalysis of photoredox and metal catalysis. Both aryl and alkyl terminal olefins can be readily converted into the desired products in good yields under visible light mediation by employing an irridium photocatalyst in combination with a copper catalyst. It is worth mentioning that potassium ethynyltrifluoroborate is also an usable alkynylation reagent for this transformation, which could afford a valuable terminal alkyne group. These products feature two distinct clickable reaction sites, which allows for efficient multiple linking of molecules by integrating the classic CuAAC click reaction with the SuFEx click reaction, and is demonstrated in molecule ligation with a natural product and a drug molecule, respectively.

A one-pot asymmetric cascade allylation/transfer hydrogenation reaction between aryl vinyl carbinols and methyl ketone-derived silyl enol ethers has been established through bimetallic Ir/Ru sequential catalysis. This protocol enables an efficient approach for the stereoselective construction of a diverse library of chiral homoallylic carbinol derivatives bearing two nonadjacent 1,3-tertiary/tertiary stereocenters. These structurally important products could be readily obtained in moderate to good yields with excellent stereocontrol (up to 85% yield, >20 : 1 dr, 99% ee), underscoring the robustness and efficiency of the dual catalytic system. Notably, this one-pot sequential process offers several important advantages, including the use of readily available starting materials, broad substrate scope, and exceptionally high levels of both diastereoselectivity and enantioselectivity. The synthetic utility is further demonstrated by its scalability and operational simplicity; a gram-scale transformation proceeds smoothly while maintaining both yield and stereoselectivity in one-pot manner. Moreover, this methodology was well utilized to realize the stereodivergent formal synthesis of the marine natural products calyxolane A and calyxolane B from the same starting materials.

The simultaneous and precise control over both alkene geometry and molecular chirality remains a formidable challenge in asymmetric synthesis, particularly within the realm of carbocation chemistry. Carbocations are notoriously difficult to tame due to their planar structure and high reactivity, which often leads to the loss of stereochemical information. Here, we report a transformative catalytic strategy that addresses this long-standing challenge by harnessing cyclopropylcarbinyl cations as programmable intermediates under the sophisticated governance of chiral super Brønsted acids. These highly reactive cations, generated in situ via the protonation of readily available precursors, do not exist as “free” species; instead, they undergo a stereospecific ring-opening rearrangement pathway that is precisely directed by a tightly associated chiral counteranion. This ion-pair catalysis model effectively decouples the stereochemical outcome from inherent substrate bias or thermodynamic equilibria. By utilizing the unique structural framework of C–H acids (such as imidodiphosphorimidates), the catalyst creates a confined chiral environment where noncovalent interactions, including London dispersion and hydrogen bonding, stabilize the transition state. This level of control enables the simultaneous installation of a defined tetrasubstituted or trisubstituted carbon center and a stereodefined double bond, achieving exceptional levels of enantioselectivity and E/Z selectivity. The synthetic utility of this method is demonstrated through the direct access to valuable 1,1-diaryl trisubstituted alkenes and complex sulfur-containing products with high stereochemical fidelity. Unlike conventional strategies that rely on expensive transition metals or extensive pre-functionalization of substrates, our approach leverages a classical S_N1-type manifold. This atom-economical process is environmentally benign, with water formed as the sole byproduct. By integrating rearrangement chemistry with the potency of super Brønsted acid catalysis, this work significantly expands the boundaries of organocatalysis. Overall, this strategy establishes a robust and general approach for the stereocontrolled synthesis of complex molecules via transient cationic intermediates, paving the way for the exploitation of high-energy reactive species in total synthesis and medicinal chemistry.

Hybrid antiperovskites have attracted tremendous research interest with unique assembly architecture, holding great promise in ferroelectricity, nonlinear optics, optoelectronic detection, etc. However, constructing hybrid antiperovskite has always been a great challenge, and the ferroelasticity within this family remains unexplored. Here, we report the first case of hybrid antiperovskite ferroelastic, (C₃H₈ON)₃(SnCl₆)Cl, designed via molecular modification. Through hydrogen-bond engineering by substituting (C₃H₆ON)⁺ cations with (C₃H₈ON)⁺, the stacking arrangement of components in lattice was reconfigured to transform a zero-dimensional precursor of (C₃H₆ON)₂SnCl₆ into a three-dimensional hybrid antiperovskite architecture. This structural reorganization successfully induces a ferroelastic phase transition with an Aizu notation of 2mF222. This work not only enriches the hybrid antiperovskite family, but also sheds new light for designing ferroic materials.

To address the critical challenges of inefficient charge separation and uncontrollable selectivity in plastic photocatalytic upcycling, a MoS₂/BiOCl heterojunction was designed. The precisely engineered interface created a built-in electric field that enhanced charge separation and optimized the oxidation pathway. Specifically, the moderate oxidation potential of MoS₂ prevents polylactic acid (PLA) mineralization, while the negative conduction band of BiOCl facilitates hydroxyl radicals (·OH) generation via oxygen reduction. The hole and ·OH establish a synergistic dehydrogenation pathway, significantly boosting both reaction rate and product selectivity. The band structure modulation induced by the interface engineering reduces the free energy change for the lactic acid in the key dehydrogenation step from +0.29 eV to –0.13 eV, turning an endergonic into a spontaneous process. Under aqueous conditions at 20 °C, the optimized catalyst exhibits 93% selectivity for pyruvic acid formation at a remarkable rate of 3.46 mmol·h^-1·g_cat.^-1, outperforming BiOCl and MoS₂ by up to 31.5-fold and 2.4-fold, respectively, ranking it among the forefront of reported non-noble-metal photocatalysts. This system achieves a 77.6% carbon conversion, while the apparent quantum efficiency is 0.23% under 420 nm irradiation. This work presents a strategy for high-selectivity in plastic upcycling under mild conditions, enabling green and precise waste conversion.

Quinolin-2(1H)-ones represent a class of privileged nitrogen-containing heterocycles widely found in natural products, pharmaceuticals, and functional materials. Traditional synthetic methods often rely on harsh conditions such as high temperatures, high CO pressures, or stoichiometric oxidants, which limit their functional group tolerance and sustainability. In this work, we report a visible-light-driven palladium-catalyzed carbonylative cyclization of o-alkynylanilines for the efficient synthesis of quinolin-2(1H)-ones under mild and oxidant-free conditions. The key innovation lies in the use of triphenylsilane (Ph₃SiH) as a mild hydrogen atom donor, enabling C–H activation and CO incorporation at ambient pressure and room temperature. The cooperative Pd(TFA)₂/Ir(ppy)₃ catalytic system, combined with TBAB as an additive, delivers the desired products in good to excellent yields with broad functional group tolerance. The protocol is applicable to a variety of substituted o-alkynylanilines, including those bearing electron-donating, electron-withdrawing, and disubstituted groups, as well as heteroaryl and cycloalkyl N-substituents. Notably, the method also extends to the synthesis of coumarin derivatives from o-alkynylphenols, further demonstrating its versatility. Late-stage functionalization of bioactive aldehydes, such as vanillin, cinnamaldehyde, and (–)-perillaldehyde, was successfully achieved, underscoring the potential for drug discovery applications. Gram-scale synthesis and further transformations, including chlorination, reductive functionalization, and photocatalytic methylation, highlight the synthetic utility of this approach. Mechanistic studies, including deuterium labeling, radical trapping, and fluorescence quenching, support a radical pathway involving photoredox-generated radical cations and Pd-hydride intermediates. This work provides a sustainable and practical platform for the construction of valuable N-heterocycles and offers new insights into silane-mediated hydrogen transfer in dual catalytic systems.

Fluorescent materials, owing to their excellent photophysical properties, are highly influential in both fundamental research and industrial applications. This study introduced the novel concept of “halogen-bonded induced emission (HIE)” for the first time, based on the unique [N···I···N]⁺ halogen bonds. Contrasting sharply with the weak fluorescence of monomers, quinoline and its derivatives demonstrate markedly enhanced photoluminescence intensity accompanied by higher quantum yields upon formation of [N···I···N]⁺ complexes. Single-crystal analysis confirmed that QL-I adopts the expected linear three-center-four-electron coordination geometry (N-I-N bond angle ~178.4°), with the two quinoline rings nearly coplanar and stacked in a slipped arrangement. This configuration effectively extends the π-conjugation while minimizing detrimental intermolecular π-π stacking. The experiments further revealed the underlying emission mechanism: the halogen bond stabilizes the excited-state energy levels, suppresses nonradiative decay pathways, thereby enhancing radiative transitions as well as overall fluorescence efficiency. Furthermore, doping the iodine complexes into poly(methyl methacrylate) (PMMA) successfully yielded highly luminescent fluorescent films. This study not only offers deep insights into the impact of the [N···I···N]⁺ halogen bond as a weak interaction in optical applications, but also provides a more convenient and efficient pathway for developing supramolecular photofunctional materials with high luminescence efficiency.

Sluggish oxygen evolution kinetics and chloride-induced corrosion remain critical barriers to the development of efficient anode catalysts for seawater electrolysis. Here, we propose a defect-engineering strategy based on sacrificial vanadium(V) doping to construct a disordered NiFe layered double hydroxide (d-NiFe(OH)_x) nanosheet electrocatalyst. During electrochemical activation, V is rapidly leached, inducing the in situ formation of abundant non-metallic defects and lattice disorder. Experimental results, in-situ characterizations combined with density functional theory (DFT) calculations reveal that the disordered structure promotes the formation and stabilization of catalytically active, defect-rich high-valent NiOOH phases, enhances the adsorption of OH^– adsorption and suppress Cl^–- induced side reactions, and activates lattice oxygen participation in the OER process, thereby ensuring long-term catalytic activity during seawater OER. As a result, the catalyst achieves an industrial-level current density of 1.0 A·cm^–2 at 1.55 V in alkaline seawater and maintains excellent stability over 160 h, with a hydrogen production cost as low as $1745 per ton. This work offers a theoretical basis for designing efficient and corrosion-resistant OER catalysts for seawater electrolysis.

Heme oxygenases catalyze C–H oxidation primarily via the oxygen rebound mechanism to form hydroxylated products. While hydroxylation is the principal pathway in iron-containing oxygenases and corresponding biomimetic systems, manganese porphyrin analogues can mediate alternative reaction pathways. The oxygen rebound step is much slower in manganese porphyrin systems, permitting radical escape and thereby enabling interception by various nucleophiles. Based on these findings, chlorination, bromination, fluorination, azidation, and isocyanation of unactivated C–H bonds have been accomplished via bioinspired oxidation reactions when related anions were introduced (such as F^–, Cl^–, Br^–, N₃^– and NCO^–). However, the iodination of hydrocarbons in biomimetic systems remains unreported. The susceptibility of I^– to oxidation by common oxidants (e.g., PhIO) to form I₂ precludes its use as a direct halogen source in biomimetic C–H functionalization. Recently, it has been found that carbon radicals generated by hydrogen atom abstraction (HAA) with a Mn(IV)-oxo porphyrin can escape the solvent cage and react with halohydrocarbon solvents (e.g., CH₂Cl₂) to form chlorinated products. Inspired by this finding, we have achieved manganese porphyrin-catalyzed C–H iodination using CHI₃ as the halogen source. Furthermore, when the halogen source was replaced with CBr₄, the bromination of unactivated C–H bonds was also accomplished. In all cases, only the halogenated products were detected, exhibiting satisfactory yields. Mechanistic studies indicate that the active intermediate, Mn(V)-oxo porphyrin complex (or Mn(IV)-oxo porphyrin complex), generates carbon radicals by abstracting hydrogen atoms from hydrocarbon substrates. These radicals undergo cage escape and ultimately react with halogen sources to form halogenated products. This strategy offers a potential route for synthesizing iodinated hydrocarbons from simple hydrocarbons under mild conditions.