Manganese-based photocatalysis has emerged as a sustainable strategy in modern organic synthesis, leveraging manganese's natural abundance, low toxicity, versatile redox behavior, and tunable coordination environments. This review classifies manganese photocatalysts into three main structural categories: (i) dinuclear Mn2(CO)10, (ii) mononuclear complexes with simple ligands (including manganese salts), and (iii) well-defined complexes supported by elaborate ligand frameworks. The article systematically summarizes their applications in a range of photocatalytic transformations, such as C─H functionalization, alkene modification, coupling reactions, and redox processes, along with relevant mechanistic insights and structure-activity relationships. While challenges remain in catalyst stability, structural diversity, and stereocontrol, manganese-based photocatalysis shows strong potential for enabling greener and more sustainable synthetic routes. By providing a clear, categorization-based overview, this review aims to encourage further developments in this rapidly evolving field.

α-Trifluoromethylated phosphonates are highly valued in medicinal chemistry and functional materials, yet their efficient synthesis remains challenging. Herein, we report a practical, transition-metal-free strategy for the rapid assembly of this important class of scaffolds via a one-pot, three-component reaction, using α-trifluoromethyl diazo compounds as key precursors together with readily accessible H-phosphites and benzyl bromides or alkyl halides. This mild reaction proceeds through a base-promoted, ordered nucleophilic attack sequence, enabling the simultaneous formation of C-C and C-P bonds and affording products bearing congested, fully substituted carbon centers in high yields (up to 98%). The selected products were predicted to have favorable pharmacokinetic properties based on in silico ADME analysis. This work provides a general synthetic route to α-trifluoromethylated phosphonates and highlights their broad application prospects in drug discovery and functional materials development.

Chiral γ-amino ketones are vital scaffolds, yet catalytic asymmetric synthesis is constrained by side reactions and remote stereocontrol. We report a copper-catalyzed addition of cyclopropanols to N-sulfonyl imines that leverages ring strain for ring opening. This mechanistically distinct platform enables efficient construction of quaternary stereocenters, affording products in up to 98% yield and 93% ee.

Simultaneously achieving high dielectric constant, low elastic modulus, and high breakdown strength in elastomer composites constitutes a critical challenge for high-performance dielectric elastomer actuators (DEAs). In this work, a synergistic strategy integrating microencapsulated multi-walled carbon nanotubes (MWCNTs) and a sandwich structure is proposed to address this dilemma. Core-shell structured melamine-formaldehyde (MF@MWCNTs) fillers were synthesized via in-situ grafting, where the insulating MF shell not only enhances the dispersion of MWCNTs but also improves interfacial compatibility within the polydimethylsiloxane (PDMS) matrix. At an ultralow filler loading of 0.5 wt.%, the MF@MWCNTs/PDMS composite exhibits a significantly enhanced dielectric constant of 9.2 at 10 kHz while retaining a low elastic modulus. Furthermore, by constructing a sandwich-structured composite (MF-P-MF) with the configuration of MF@MWCNTs/PDMS-PDMS-MF@MWCNTs/PDMS, a remarkable synergistic improvement in breakdown strength is achieved, reaching 103.4 V/μm—an 85% enhancement compared to the single-layer composite filled with pristine MWCNTs. This performance enhancement is attributed to the combined effects of the MF shell’s scattering on electrical tree channels and the barrier function of the middle PDMS layer. Consequently, the optimized sandwich-structured actuator demonstrates a bending deformation that is 200% higher than that of pure PDMS under the same driving field. This work provides a novel and effective design paradigm for the development of advanced dielectric elastomers with integrated high electromechanical performance, holding great potential for applications in soft robotics and flexible electronics.

Despite growing interest in 3d transition metals for photoredox catalysis, manganese remains markedly underexplored in this domain. The advancement of Mn-based photochemical asymmetric transformations has been significantly hindered by the metal's extensive range of accessible oxidation states (from -3 to +7), intricate excited-state redox behavior, and the propensity to form highly reactive transient species─factors that collectively undermine precise stereochemical control. To overcome these limitations, we introduce a synergistic dual-catalytic system that integrates a unique Mn(IV)/Mn(III) dual-excitable complex featuring N-heterocyclic carbene (NHC) ligands with a chiral cobalt bisoxazoline complex. This well-defined manganese complex enables mechanistically distinct and controllable radical pathways through excitation at different oxidation states─Mn(IV)* and Mn(III)*─allowing each excited state to be selectively harnessed with cobalt-mediated stereocontrol. This adaptive strategy facilitates two challenging enantioselective transformations: asymmetric alkylation of acyclic α-imino esters to construct quaternary stereocenters, and enantioselective protonation to form tertiary stereocenters. A wide range of α-tertiary and α-secondary amino acid derivatives were obtained in up to 99% yield with excellent enantioselectivity (up to 99:1 er). Notably, the system exhibits pronounced nonlinear stereochemical amplification, delivering high-fidelity enantioselection (up to 99:1 er) even when using a partially enriched chiral ligand (65:35 er). By leveraging earth-abundant metals and visible-light activation, our approach provides a sustainable and versatile platform for synthesizing high-value chiral building blocks, with promising implications for pharmaceutical and materials science.

The selective and consecutive cleavage of C(sp3)─C(sp3) bonds while simultaneously governing chemo-, regio-, and stereoselectivity constitutes a long-standing unresolved challenge in synthetic chemistry. Here, we present a visible light-driven copper catalysis platform that surmounts this obstacle. A chiral bisoxazoline copper complex acts as a multifunctional catalyst, and a tailored sodium sulfoxylate additive modulates the metal coordination sphere, altogether eliminating the requirement for an external photosensitizer. This streamlined system promotes twofold C(sp3)─C(sp3) fragmentation of cyclobutanols and subsequent coupling with imines to construct quaternary carbon stereocenters, releasing ethylene as the sole byproduct. Integrated experimental and computational investigations delineate an unprecedented cascade mechanism: photoinduced ligand-to-metal charge transfer (LMCT) initiates strain-release ring opening, a copper-mediated β-cleavage executes the second fragmentation, and a highly enantioselective radical addition to the imine completes the stereodefined assembly. The sodium sulfoxylate additive proves indispensable for rerouting the pathway toward the second cleavage over premature radical trapping and elevating enantioselectivity to as high as 99% ee. By demonstrating rigorous kinetic command over multiple C(sp3)─C(sp3) cleavages within a single cascade, this work establishes a new paradigm for photochemical asymmetric synthesis.

Phosphorus‐centered radicals hold transformative potential for organophosphorus synthesis, yet their configurational lability and distinctive reactivity profiles have historically restricted their application in asymmetric catalysis. Herein, we report a copper‐photoredox catalytic system that enables the stereoselective generation of copper‐bound P‐centered radicals and their subequent stereoretentive transformations within a well‐defined chiral environment. The synergistic approach achieves unprecedented kinetic resolutions of racemic H‐phosphinates with α‐trifluoromethyl styrenes or gem ‐difluorostyrenes, delivering 85 fluorine‐containing P‐chiral phosphinates with up to 98% ee. The method thereby bridges a synthetic gap for these previously inaccessible, pharmacologically significant compounds. Mechanistic and computational studies reveal a stereochemical relay: enantiodiscriminatory binding of racemic substrates, photoinduced ligand‐to‐metal charge transfer (LMCT) for radical generation, and stereoretentive bond formation. By reconciling radical reactivity with stereochemical fidelity, our strategy establishes metallaphotoredox catalysis as a versatile paradigm for heteroatom‐centered stereochemistry.

The hydroacylation of unsaturated pi-systems with aldehydes offers a direct and atom-economical route for introducing both a hydrogen atom and an acyl group into an organic molecule. Whereas hydroacylation reactions with alkanes and alkenes are well established, transformations involving imines have been much less successful. Existing approaches often favor C-C bond formation over C-N bond formation, due to the inherent properties of imines and acyl radicals. We present a photochemical approach that specifically targets N-sulfonylimine esters in combination with aldehydes. This reaction is facilitated by a decatungstate-salt-mediated double hydrogen-atom-transfer (HAT) activation that uniquely promotes the formation of C-N bonds under mild and simple conditions. Our method permits the efficient synthesis of a broad spectrum of distinctive N-sulfonyl N-carbonyl amide products with exclusive regioselectivity. We expect this streamlined method to expand the synthetic toolkit available for constructing complex nitrogen-containing compounds.

2H‐Indazole scaffolds represent privileged structural motifs prevalent in a wide range of bioactive compounds and pharmaceutical agents. Despite their significance, conventional synthetic approaches to 2H‐indazole derivatives often suffer from limitations such as harsh reaction conditions, the use of expensive or toxic catalysts, and multistep procedures. To address these challenges, we report a cost‐effective, environmentally benign, and one‐pot strategy for the synthesis of biologically and synthetically valuable 3‐arylamino‐2‐aryl‐2H‐indazoles. This method employs readily available o‐nitrobenzyl alcohols as key building blocks and utilizes a Lewis acid iron salt as a catalyst under visible light irradiation, harnessing the excited‐state reactivity of the substrates. The transformation proceeds efficiently without the need for precious metal catalysts, external oxidants, or additives and operates under mild and sustainable conditions. The protocol enables the construction of structurally complex 2H‐indazoles, including those embedded in medium‐sized rings. Notably, the synthesized 3‐arylamino‐2‐aryl‐2H‐indazoles exhibit a selective fluorescence quenching response toward hypochlorite, highlighting their potential as an effective probe for ClO− detection.

Covalent organic frameworks (COFs) have latterly emerged as a promising platform for devising electrode materials used to acquire high‐performance lithium‐ion batteries (LIBs). However, the preparation of COFs with fast redox kinetics, high‐efficiency utilization of active sites, superior stability, and high conductivity remains a challenge. Herein, a thiophene‐based bipolar‐type COFs (denoted as TT‐TPDA‐COF) featuring extended conjugation, rich multiple redox‐active sites (C─S, C─N, and C═N), and hierarchical micro‐mesoporosity is synthesized. TT‐TPDA‐COF exhibits significantly increased density of redox‐active sites and enhanced electrical conductivity compared with its corresponding counterpart (Np‐TPDA‐COF). Remarkably, when TT‐TPDA‐COF is used as LIBs cathode, it shows exceptional specific capacity up to 309 mA h g −1 at 200 mA g −1 , significantly surpassing that of Np‐TPDA‐COF (195 mA h g −1 at 200 mA g −1 ), high energy density of 714 W h kg −1 , superb rate property (182 mA h g −1 at 5000 mA g −1 ), and impressive capacity preservation of 84.3% after 5000 cycles at 5000 mA g −1 . Additionally, the predictable application of TT‐TPDA‐COF for prototype batteries has been proved by the high‐performance dual‐ion full cells assembled by using TT‐TPDA‐COF as cathode. Furthermore, the dual‐ion storage mechanism of TT‐TPDA‐COF is comprehensively revealed by in/‐ex situ studies and theoretical calculations.

Hydrogen peroxide (H 2 O 2 ) is a vital industrial chemical extensively utilized in textiles, pharmaceuticals, and disinfection. Solar-driven photocatalytic technology depending on photocatalysts with matched energy band structure for simultaneously driving both O 2 reduction and water oxidation half-reactions, without necessary use of any sacrificial agent, enables green H 2 O 2 synthesis from O 2 and/or H 2 O, offering a low-energy and simple-operation process without secondary pollution while avoiding safety and environmental risk of conventional methods. Herein, a novel acylhydrazone-linked 2D COF, COF-S-OH , was prepared from benzo[1,2- b :3,4- b ':5,6- b '']trithiophene-2,5,8-tricarbaldehyde and 2,3-dihydroxysuccinohydrazide. Both experimental and theoretical analyses reveal that introduction of benzotrithiophene units and hydroxyl groups enhances the electron donor-acceptor effect in COF-S-OH , optimizes the light-harvesting and adsorption capacities to O 2 and H 2 O, and particularly enables efficient proton transfer, thereby synergistically improving photogenerated charge carrier separation and surface reaction efficiency. Consequently, COF-S-OH achieves an exceptional H 2 O 2 production rate of 10.2 mmol g −1 h −1 with a solar-to-chemical conversion efficiency of 2.1%, superior to all the thus far reported photocatalysts for H 2 O 2 synthesis. This work underscores the critical importance of carrier separation, active site, and proton supply in photocatalytic H 2 O 2 generation, providing guidance for designing and fabricating next-generation photocatalysts.

Regiodivergent asymmetric synthesis provides a powerful strategy for generating structurally diverse chiral molecules from common starting materials. However, achieving precise control over both regio- and stereoselectivity in radical-mediated processes remains a formidable challenge, largely due to the transient nature and flexibility of radical intermediates. To tackle this longstanding issue, we have developed a cooperative catalytic platform that integrates photoinduced hydrogen atom transfer (HAT) with chiral copper catalysis. This dual-catalyst system enables regiodivergent and enantioselective C(sp(3))-H functionalization of N-aryl glycine derivatives using simple hydrocarbons as alkylating agents. Through systematic modulation of chiral ligands, additives, and other reaction parameters, we have achieved switchable formation of either C(sp(3))-C(sp(3)) or C(sp(3))-N bonds, leading to the selective synthesis of C- or N-alkylated products. The reactions proceed with high efficiency (up to 92% yield), excellent regiocontrol (>20:1 rr), and outstanding enantioselectivity (up to 96% ee). Importantly, this methodology facilitates site-selective alkylation of biologically relevant scaffolds and demonstrates tunable regioselectivity under mild photochemical conditions. Thus, it establishes a new paradigm for stereocontrolled bond construction in complex molecular architectures.

Regiodivergent asymmetric synthesis represents a transformative strategy for the efficient generation of structurally diverse chiral products from a single set of starting materials, significantly enriching their enantiomeric composition. However, the design of radical-mediated regiodivergent and enantioselective reactions that can accommodate a wide range of functional groups and substrates has posed significant challenges. The obstacles primarily lie in switching the regioselectivity and achieving high enantiodiscrimination, especially when dealing with high-energy intermediates. To address these issues, we have developed a new catalytic system that integrates photoinduced hydrogen atom transfer (HAT) and chiral copper catalysis, involving the fine-tuning of chiral ligands, additives, and other reaction parameters. The strategy facilitates regiodivergent and enantioselective cross-couplings between N-aryl glycine ester/amide derivatives and abundant hydrocarbon feedstocks through strong C(sp3)-H bond activation. This approach allows for the controlled and stereoselective formation of C(sp3)-C(sp3) and C(sp3)-N bonds, yielding a rich variety of C- or N-alkylated glycine esters and amides with commendable yields (up to 92% yield), exclusive regioselectivities (typically >20:1 rr), and high enantioselectivities (up to 96% ee). Our methodology not only provides a promising avenue for the stereoselective incorporation of alkyl functionalities onto specific sites of biologically significant molecules but also offers a practical approach for regioselectivity switching while simultaneously achieving high asymmetric induction within photochemical reactions.

Visible-light-induced transition-metal catalysis is becoming essential in organic synthesis, offering sustainable and mild routes to complex molecules. Among these, photoredox-mediated cobalt catalysis has emerged as a particularly promising approach. Cobalt’s capacity to direct stereochemistry stems from its diverse redox behavior, geometric flexibility, and the ability to transition between octahedral and tetrahedral configurations. Additionally, its redox-adaptive ligand fields and spin-state plasticity play crucial roles. Recent advances have produced efficient catalytic systems capable of novel photochemical transformations, particularly in synthesizing enantiomerically enriched compounds. However, challenges remain, particularly concerning the regulation of high-energy intermediates and the mitigation of competing thermal processes. Achieving stringent stereoselectivity remains a critical hurdle, requiring integration of coordination chemistry and photophysics. This review traces the development of photoredox-mediated cobalt catalysis, emphasizing recent progress in asymmetric catalysis. By analyzing mechanisms and applications, we aim to highlight both the potential and current limitations, thereby guiding future research and innovation in photoredox-mediated cobalt catalysis field.

The hydroacylation of unsaturated π-systems with aldehydes offers a direct and atom-economical route for introducing both a hydrogen atom and an acyl group into organic molecules. While hydroacylation reactions with alkanes and alkenes are well-established, transformations involving imines have been much less successful. Existing approaches often favor C-C bond formation over C-N bond formation due to the inherent properties of imines and acyl radicals. In this study, we present a photochemical approach that specifically targets N-sulfonylimine esters in combination with aldehydes. This reaction is facilitated by decatungstate salt-mediated double hydrogen atom transfer (HAT) activation, which uniquely promotes the formation of C-N bonds under mild and simple conditions. Our method allows for the efficient synthesis of a broad spectrum of distinctive N-sulfonyl-N-carbonyl amide products with exclusive regioselectivity. We anticipate that this streamlined method will expand the synthetic toolkit available for constructing complex nitrogen-containing compounds.

The direct construction of polycyclic arenes through ring formation using simple building blocks is highly appealing but remains challenging in organic chemistry. In this study, we introduce an efficient cascade reaction that combines dearomatizing photocyclization with oxidative aromatization, driven by organophotocatalysis. Conducted under mild, transition-metal-free conditions, this reaction seamlessly converts styrene derivatives into a diverse array of functionalized polycyclic aromatic compounds with good yields and regioselectivity. This approach provides a straightforward and economical route to valuable polycyclic arenes, starting from readily available and abundant styrene derivatives.

Copper-catalyzed multicomponent reactions (MCRs) have garnered growing attention from synthetic chemists, due to their compelling attributes, such as cost-effectiveness, low toxicity, versatility in orchestrating one or two-electron processes, and the extraordinary capacity to enhance molecular complexity in a single step. The synergistic combination of these reactions with photocatalysis paves the way for novel reaction pathways, offering opportunities for new transformations executed under gentler, more environmentally-friendly conditions. Copper's catalytic prowess is further underscored by its adept management of key intermediate stability and reactivity within photochemical frameworks, a testament to its multifaceted utility. Furthermore, the strategic introduction of suitable chiral ligands enables photoinduced copper-catalyzed asymmetric MCRs, streamlining the synthesis of a variety of new chiral compounds in an atom- and step-economical manner. This review aims to comprehensively encapsulate the recent advancements in photoinduced copper-catalyzed MCRs, including racemic and asymmetric fashions, dissecting the underlying reaction mechanisms, and charting a course for future explorations in this promising field.

The effective control over the rotary motions of molecular rotors still remains an enormous challenge. Herein, mixed (phthalocyaninato)(porphyrinato) rare-earth triple-decker complexes (R)-/(S)-Eu and (R)-/(S)-Y have been designed and investigated as a new type of molecular rotors with a phthalocyanine ligand as the rotator and a strapped bisporphyrin ligand as the stator. The rotational rates and thermodynamic parameters of the rotors were determined through variable-temperature 1H NMR experiments, revealing a higher rotational rate and a reduced rotational barrier for (R)-Y, in comparison to those of (R)-Eu. Variable-temperature CD experiments demonstrated that these chiral molecular rotors exhibited temperature-dependent chiroptical properties. Upon elevating the temperature, the reduction of CD intensity is closely related to the conformational perturbation involving the increased rotational rate. The DFT calculation results further elucidate that the increased rotational rate of the phthalocyanine rotator in (R)-Y can be attributed to the reduced steric interaction between the phthalocyanine rotator and the binaphthol linkage of the bisporphyrin stator owing to the diminished radius from Eu(III) to Y(III). Thus, effective control over the rotary motions can be realized by tuning the steric interactions involving adjustment of center metal ions in this new type of molecular rotors.

Fabricating COFs-based electrocatalysts with high stability and conductivity still remains a great challenge. Herein, 2D polyimide-linked phthalocyanine COF (denoted as NiPc-OH-COF) is constructed via solvothermal reaction between tetraanhydrides of 2,3,9,10,16,17,23,24-octacarboxyphthalocyaninato nickel(II) and 2,5-diamino-1,4-benzenediol (DB) with other two analogous 2D COFs (denoted as NiPc-OMe-COF and NiPc-H-COF) synthesized for reference. In comparison with NiPc-OMe-COF and NiPc-H-COF, NiPc-OH-COF exhibits enhanced stability, particularly in strong NaOH solvent and high conductivity of 1.5 x 10(-3) S m(-1) due to the incorporation of additional strong interlayer hydrogen bonding interaction between the O-H of DB and the hydroxy "O" atom of DB in adjacent layers. This in turn endows the NiPc-OH-COF electrode with ultrahigh CO2-to-CO faradaic efficiency (almost 100%) in a wide potential range from -0.7 to -1.1 V versus reversible hydrogen electrode (RHE), a large partial CO current density of -39.2 mA cm(-2) at -1.1 V versus RHE, and high turnover number as well as turnover frequency, amounting to 45 000 and 0.76 S-1 at -0.80 V versus RHE during 12 h lasting measurement.

The synthesis of α-tertiary amino acids (ATAAs), which are pivotal components in natural metabolism and pharmaceutical innovation, continues to attract significant research interest. Despite substantial advancements, the pursuit of a facile, versatile, and resource-efficient methodology remains an area of active development. In this work, we introduce a visible light-triggered three-component reaction involving readily available nitrosoarenes, N-acyl pyrazoles, and allyl or (bromomethyl)benzenes under mild conditions. This approach enables the straightforward assembly of a wide array of ATAA derivatives (42 examples) in commendably high yields (up to 89 %). Mechanistic investigations elucidate that the reaction proceeds through a dehydration condensation between nitrosoarenes and N-acyl pyrazoles to generate ketimine intermediates. This is followed by a light-driven halogen atom transfer (XAT) process and a radical addition, culminating in the formation of the desired products. The approach showcases excellent functional group compatibility and late-stage derivatization potential, offering new insights and avenues for the synthesis of ATAA analogs.