Accounts of Chemical Research最新文献

{"title":"Harnessing Composition and Sequence in Carbonylative Polymerization of Olefin for Tailored Material Properties","authors":"Shi-Yu Chen, Jun Li, Ye Liu","doi":"10.1021/acs.accounts.6c00616","DOIUrl":"10.1021/acs.accounts.6c00616","url":null,"abstract":"<p>Commercial polyolefin plasticsare indispensable to modern society;however, their chemical inertness renders them environmentally persistent,thereby contributing to severe plastic pollution and ecological challenges.Accordingly, the development of commercially viable degradable materialswith performance comparable to or even superior to that of conventionalpolyolefins has received substantial interest. Polyketones representa compelling alternative: they are synthesized from commercially availableolefin feedstocks and low-cost carbon monoxide (CO) and exhibit excellentmechanical strength, high thermal stability, superior barrier properties,and inherent photodegradability arising from their regularly spacedin-chain carbonyls. Despite the industrialization of palladium-catalyzedcarbonylative polymerization, this reaction remains largely undeveloped,constrained by the reliance on a precious palladium catalyst, thepoisoning effect of CO on transition metals, and the kinetic preferencefor CO insertion, which results in limited polymer compositions andsequence structures.</p><p>This Account summarizes our systematicresearch progress in catalystdesign, structural regulation, and material properties for carbonylativepolymerization. Building on the fundamental mechanistic differencebetween olefin homopolymerization and olefin/CO copolymerization,we have custom-designed and developed three classes of [P,O]-typeligand platforms: diphosphazane monoxide (PNPO), phosphine-sulfonate(PSO), and bisphosphine monoxide (BPMO). Their applications in Earth-abundantnickel-catalyzed carbonylative polymerization of ethylene reveal thatthe electron-donating ability of the ligands, rather than steric hindrance,could alleviate CO poisoning to the metal center and exert a dominanteffect on catalytic activity and polymer molecular weight. To addressthe limitation in polymer composition, we have realized the firstnickel-catalyzed carbonylative copolymerization of ethylene and propylene.Further extension to diverse <em>α</em>-olefins andpolar monomers has greatly expanded the accessible polymer compositions,enabling the resulting polyketones to evolve from conventional resinsand fibers into ultrastrong hot-melt adhesives and elastomers. Modulationof electronic asymmetry in [P,O]-Pd catalyst systems has enabled chainsequence control through nonalternating copolymerization to overcomethe kinetic preference for CO insertion, yielding precisely tunablecarbonyl content and uniform distribution along the polymer backbone.This nonalternating copolymerization produces a unique multiblockarchitecture integrating short polar segments and extended nonpolarmethylene sequences. Such a multiblock copolymer could act as a robustcompatibilizer for polyethylene/nylon blends, converting inherentlybrittle materials into mechanically tough composites. The introductionof true phosphorus chirality afforded a series of <em>P</em>-chirogenic palladium catalysts, which exhibited unprecedented enantios","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"59 19","pages":"3267–3281"},"PeriodicalIF":18.0,"publicationDate":"2026-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149050303","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Chemical Imaging of MXenes with X-ray Microscopy","authors":"Namrata Sharma, Louis Godeffroy, Tristan Petit","doi":"10.1021/acs.accounts.6c00324","DOIUrl":"10.1021/acs.accounts.6c00324","url":null,"abstract":"<p>Chemical imaging combines microscopy with spectroscopy to achievea chemical contrast, enabling the identification of different chemicalspecies with high spatial resolution. This capability is particularlyvaluable for the characterization of composite and heterogeneous materials,as well as for probing chemical reactions that are spatially segregatedat the micro- or nanoscale. Representative examples include catalyticprocesses that locally modify the state of a catalyst, or batteryparticles that charge nonuniformly during cycling.</p><p>Chemicalimaging can be implemented using scanning probe, optical,electron, or X-ray spectromicroscopy techniques, each providing distinctforms of chemical contrast. Scanning probe and optical methods primarilyprobe valence electrons or vibrational modes, offering high chemicalsensitivity, whereas electron and X-ray techniques typically probecore-level excitations, providing element-specific information. Thelatter also enable higher spatial resolution, as electrons and X-rayshave much shorter wavelengths than visible light (typically <10nm versus ∼400 nm).</p><p>Among these approaches, X-ray-basedmethods are particularly powerfulfor direct, label-free chemical imaging due to their high elementaland site specificity. They are also significantly less invasive thanelectron-beam techniques. The soft X-ray range (ca. 100–2000eV) is especially relevant, as it enables the selective excitationof the K-edge of light elements such as carbon, oxygen, and nitrogen,as well as the L- or M-edge of transition metals. Despite these relativelylow photon energies, spatial resolutions down to ∼10 nm canbe routinely achieved using standard X-ray optics.Moreover, the informationdepth can be tuned through the detection mode. For instance, photoemission-basedtechniques such as X-ray photoemission electron microscopy (X-PEEM)provide high surface sensitivity, whereas transmission-based methodssuch as scanning transmission X-ray microscopy (STXM) probe the bulkof the material that is though limited to thin samples. Finally, thecomparatively large penetration depth of X-rays, relative to electrons,enables the use of <em>in situ</em> cells to investigate chemicalprocesses under realistic conditions.</p><p>In this Account, we presentrecent advances in X-ray chemical imaging,highlighting our work on two-dimensional transition-metal carbidesknown as MXenes. These materials are particularly well-suited forsuch approaches due to their rich surface chemistry, flat geometry,and micrometer-sized flakes. MXenes have attracted growing interestacross a wide range of applications, including electromagnetic interferenceshielding, sensing, and energy storage. They adopt a M<sub>n+1</sub>X<sub>n</sub>T<sub><em>x</em></sub> layered structure, whereM is a transition metal, X is carbon and/or nitrogen, and T<sub><em>x</em></sub> denotes mixed surface terminations, which can beselectively imaged by (soft) X-ray techniques. This account focusesmainly on Ti<su","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"59 19","pages":"3023–3035"},"PeriodicalIF":18.0,"publicationDate":"2026-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148973729","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Functional Bond-Selective Microscopy: Physically Informed Insights in Chemistry and Biology","authors":"Philip A. Kocheril, Ryan E. Leighton, Noor Naji, Dongkwan Lee, Lu Wei","doi":"10.1021/acs.accounts.6c00380","DOIUrl":"10.1021/acs.accounts.6c00380","url":null,"abstract":"<p>Biological systems are immenselycomplex, comprising diverse molecularspecies organized across multiple spatial and temporal scales. Throughintricate networks of tightly regulated chemical reactions, cellsare able to maintain homeostasis, respond to environmental stimuli,and meet energetic demands. Despite massive technological advancesspanning many decades, a significant gap still exists in our understandingof how biochemical networks are locally regulated in living systems.Fundamental physicochemical parameters such as concentration, pH,temperature, and electrostatics, which ultimately govern chemicalreactivity, remain challenging to image quantitatively, particularlyin live cells. We argue that developing methods capable of quantitativelyimaging these physicochemical parameters is not only essential forinterrogating the regulation of biochemical reaction networks butalso provides a rich framework for uncovering hidden, physically informedinsights in chemistry and biology.</p><p>To image chemical reactionsin a biological context is a highlydemanding task; few methods exhibit the necessary biocompatibility,spatial resolution, sensitivity, molecular specificity, and quantitativereporting capacity to access subcellular chemical information. Amongexisting optical methods, vibrational spectroscopy provides a naturalcontext for understanding chemical reactions in cells, since molecularvibrations serve as chemical “fingerprints”, reportingquantitatively on the formation, breaking, and interactions of chemicalbonds. Despite this enormous potential, conventional vibrational imagingfaces significant challenges in quantifying chemical kinetics anddynamics in cells. Endogenous biomolecules exhibit highly overlapped,convoluted spectra, largely prohibiting specific molecular identification.Moreover, conventional techniques, generally based on infrared (IR)absorption or Raman scattering, have limited sensitivity, and in thecase of IR absorption, coarse spatial resolution while operating atthe diffraction limit, obscuring subcellular detail. As such, thereis a significant need for vibrational spectro-microscopies with improvedmolecular specificity, sensitivity, and spatial resolution.</p><p>Coupling novel nonlinear optical strategies, which provide highersensitivity and spatial resolution, with engineered vibrational probes,which afford higher molecular specificity and functionality, has provenfruitful in addressing these longstanding challenges in vibrationalimaging and enabling functional bond-selective imaging. In this Account,we highlight recent work from our group toward quantitative measurementsof physicochemical observables in biological systems. We first demonstratethe utility of small vibrational probes (deuterium labeling and alkynetagging) with stimulated Raman scattering (SRS) microscopy for absoluteconcentration determination in protein aggregates and local pH sensingvia hydrogen–deuterium exchange. We then discuss the developmentof two new imag","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"59 19","pages":"3063–3075"},"PeriodicalIF":18.0,"publicationDate":"2026-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148933844","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Cation-Controlled eFluorination: Engineering Reactive Intermediates for Selective C–F Bond Formation","authors":"Hamid Salehzadeh, Ewan Tushkanov, Kevin Lam","doi":"10.1021/acs.accounts.6c00404","DOIUrl":"https://doi.org/10.1021/acs.accounts.6c00404","url":null,"abstract":"<p>Selective C–F bond formation remainsa fundamental challengein synthetic chemistry as fluorination reactions often involve highlyreactive intermediates, competing decomposition pathways, and fluoridesources whose effective reactivity depends strongly on their chemicalenvironment. Although conventional fluorination methods have enabledbroad applications in medicinal chemistry and agrochemical science,many approaches rely on stoichiometric oxidants or electrophilic fluorinatingreagents, which limit selectivity, functional-group tolerance, andoperational simplicity. Electrochemical synthesis offers a complementarystrategy in which electrons function as traceless redox reagents,enabling controlled generation of reactive intermediates under comparativelymild conditions.</p><p>A central theme emerging from modern electrochemicalfluorinationis that selective C–F bond formation depends less on the intrinsicnucleophilicity of fluoride and more on the controlled generation,stabilization, and interception of cationic intermediates. Acrossdiverse reaction classes, productive fluorination occurs when electrochemicalconditions, substrate structure, solvent environment, and fluoridespeciation are collectively matched to prolong intermediate lifetimewhile suppressing overoxidation, elimination, rearrangement, or fragmentationpathways. In this context, fluoride availability is not a fixed propertybut is governed by hydrogen bonding, ion pairing, solvation, and theidentity of the fluoride source itself, including poly(HF) salts,tetrafluoroborate systems, and metal fluoride complexes.</p><p>Inthis Account, we summarize recent advances in electrochemicalfluorination mediated by stabilized radical cation and carbocationintermediates with an emphasis on contributions from our group. Wediscuss how heteroatom substitution, π-system delocalization,neighboring-group participation, and control of electrochemical parameterscan be leveraged to direct selective fluoride capture. Representativesystems include sulfur-, oxygen-, and nitrogen-assisted fluorinationmanifolds, radical-polar crossover fluorination of benzylic and tertiarysubstrates, fluorination involving vinyl and arene radical cations,and electrogenerated hypervalent iodine mediators that enable fluorinationthrough related oxidative pathways.</p><p>Attention is devoted tomechanistic principles that unify thesetransformations. Collectively, the studies show that electrochemistryprovides additional tunability; however, oxidation mode, medium, fluoridespeciation, mass transport, and intermediate lifetime remain interdependent.Cyclic voltammetry, radical-trapping, isotope-labeling, and reaction-environmentstudies increasingly frame electrochemical fluorination as a parameter-matchingproblem rather than a collection of isolated reaction classes.</p><p>Beyond reaction development, these advances establish broader conceptualfoundations for electrosynthetic fluorination. Continued progresswill require a better understand","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"59 19","pages":"3090–3101"},"PeriodicalIF":18.0,"publicationDate":"2026-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149124780","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Superphanes: From Synthetic Breakthroughs to Supramolecular Hosts and Functional Molecular Materials","authors":"Wei Zhou, Aimin Li, Qing He","doi":"10.1021/acs.accounts.6c00466","DOIUrl":"10.1021/acs.accounts.6c00466","url":null,"abstract":"<p>The development of host moleculeshas long been central to theprogress of supramolecular chemistry and the design of advanced functionalmaterials. Over the past several decades, a wide variety of host architectures─includingcrown ethers, cyclodextrins, cucurbiturils, calixarenes, calixpyrroles,pillararenes, beltarenes, covalent organic cages, and metal–organiccages─have been devised and exploited for molecular recognition,sensing, transport, self-assembly, and catalysis. Despite these advances,the continued search for structurally unique and functionally versatilemolecular systems remains essential to achieving new levels of precisionin host–guest chemistry and to driving the development of next-generationfunctional materials.</p><p>Superphanes, defined by two face-to-facebenzene rings clampedby six bridging linkers, represent a structurally distinctive classof molecular constructs. First conceptualized by Vögtle in1972 and synthesized by Boekelheide in 1979 as models for π–πinteractions, superphanes remained largely unexplored for decadesdue to formidable synthetic challenges. Only two covalent superphaneswithout accessible voids and a handful of metal-coordinated analogueshave been described, with investigations restricted primarily to synthesisand structural characterization. Importantly, their potential in host–guestchemistry and functional materials applications went unrealized, hinderedby both the lack of practical synthetic access and the long-standingperception that these frameworks offered no accessible cavities.</p><p>Around the same time, our group, in parallel with Badjićand co-workers, independently developed dynamic imine-condensationstrategies for accessing imine-based superphane-type architectures.Building on this foundation, our group further advanced superphanechemistry by establishing efficient gram-scale synthetic access throughdynamic imine assembly, followed by postsynthetic stabilization viareduction or oxidation. Distinguished by six bridging linkers thatgenerate a nearly enclosed three-dimensional cavity with extreme confinement,superphanes offer unique advantages, including guest incarceration,enhanced binding affinities, super cage effects, and a uniformly distributedarray of binding sites. Their dense, symmetric architectures provideprecise control over molecular recognition events that surpasses manytraditional macrocycles and cages.</p><p>In this Account, we summarizerecent breakthroughs in superphanechemistry, including scalable dynamic covalent syntheses, presyntheticfunctionalization, postsynthetic modifications, and fine-tuning ofthe cavity environment. We further highlight how these synthetic anddesign advances have enabled a wide spectrum of applications, rangingfrom fundamental host–guest chemistry to practical uses inenvironmental remediation, selective recovery of high-value resources,photocatalysis, energy storage, and desalination. Notably, superphane-basednonporous amorphous sorbent (<strong>NAS</stro","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"59 19","pages":"3102–3117"},"PeriodicalIF":18.0,"publicationDate":"2026-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148822359","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Chemical-Energy-Driven Dioxygen Activation in Aqueous Solution: A Green Advanced Oxidation Strategy for Environmental Remediation","authors":"Chengyu Duan,&nbsp;Yang Peng,&nbsp;Zhuofeng Hu,&nbsp;Jingyun Fang","doi":"10.1021/acs.accounts.6c00402","DOIUrl":"10.1021/acs.accounts.6c00402","url":null,"abstract":"<p>Reactive oxygen species (ROS), such as ·OH,·O₂^–, and ¹O₂, play dominantroles in advanced oxidation processes for environmental remediation.Dioxygen activation provides a green route for ROS generation in aqueoussystems because molecular oxygen is abundant, inexpensive, and environmentallybenign. Compared with photoactivation or electroactivation, chemical-energy-drivenactivation without external energy input is particularly attractivefor low-energy water treatment, especially under conditions whereelectrical power is limited or natural solar irradiation is unstable.Understanding and controlling chemical-energy-driven dioxygen activationis therefore important for developing sustainable water-treatmenttechnologies that minimize external energy consumption and the handlingof concentrated oxidants.</p><p>This Account focuses on homogeneousand heterogeneous dioxygenactivation and discusses the key factors governing activator selection,ROS generation, and contaminant degradation in aqueous environmentalremediation. Most reported oxygen activation systems proceed throughsequential one-electron reduction, in which O₂ is firstconverted to ·O₂^– and then furthertransformed into H₂O₂ and ·OH. Therefore,·O₂^– acts as an intermediate orprecursor in systems, whereas ¹O₂ occurs lessfrequently.</p><p>Chemical energy-driven dioxygen activation has beenshown to degradediverse contaminants, including dyes, sulfonamides, nonsteroidal anti-inflammatorydrugs, quinolone antimicrobials, benzene, phenolics, and herbicides.To further improve the activation efficiency, three strategies arerecommended: introducing oxygen vacancies, constructing gas–liquid–solidtriphase reaction interfaces, and anchoring uniformly dispersed activesites on electron-rich supports. Collectively, these insights deepenthe mechanistic understanding of dioxygen activation and provide practicaldesign principles for the development of efficient, durable, and low-energyprocesses for environmental remediation.</p>","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"59 19","pages":"3076–3089"},"PeriodicalIF":18.0,"publicationDate":"2026-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148973725","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Ligand Exchange on Zr/Hf-Oxo Clusters: Mechanistic Insights and Implications for Catalysis","authors":"Kilian Declerck,&nbsp;Ajmal Roshan Unniram Parambil,&nbsp;Nada D. Savić,&nbsp;Jonathan De Roo,&nbsp;Tatjana N. Parac-Vogt","doi":"10.1021/acs.accounts.6c00369","DOIUrl":"https://doi.org/10.1021/acs.accounts.6c00369","url":null,"abstract":"<p>Atomically precise group IVmetal-oxo clusters, consisting of structuredZr/Hf oxo nodes capped by labile ligands, are emerging as versatilecatalysts at the interface of homogeneous and heterogeneous chemistry.Their catalytic activity arises from the inherent Lewis acidity andoxophilicity associated with the metal centers, which enable coordinationto electron-donating functional groups such as carboxylates, phosphates,and amides. As a result, metal-oxo clusters can catalyze a broad rangeof bond activation and transformation reactions, including (trans)esterificationand hydrolysis. Discrete metal-oxo clusters undergo rapid surfaceligand exchange that governs substrate binding, activation, and productrelease. By tuning the identity, number, and lability of these ligands,the accessibility of Lewis acidic sites can be controlled, therebymodulating reactivity toward amide bond hydrolysis in peptides andproteins, a benchmark reaction that sensitively probes how ligandsregulate substrate access and binding. In addition, Zr/Hf-oxo clustersdisplay tunable solubility, enabling catalysis under both homogeneousand heterogeneous conditions. Using representative soluble and insolubleZr/Hf-oxo clusters, we show that ligand dynamics critically modulatereactivity both in solution and at solid–liquid interfaces.Specifically, we present an overview of mechanistic insights focusingon: (i) the soluble Zr₆ cluster, where ligand exchangedrives reactivity, (ii) the insoluble Zr₁₇ and Hf₁₈ clusters, where the ligand shell modulates the reactivity by influencingadsorption–desorption dynamics, and (iii) a comparative studyof soluble and insoluble Hf₁₂ clusters, highlighting howligand shell occupation controls reactivity across phases. Together,these studies establish ligand exchange at cluster surfaces as a keydesign parameter to tune catalytic activity and provide a basis forthe development of next-generation cluster catalysts with enhancedstability, selectivity, and recyclability.</p>","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"59 19","pages":"3050–3062"},"PeriodicalIF":18.0,"publicationDate":"2026-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149124736","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Dynamic Through-Space Interactions: A Unifying Framework for Aggregation-Induced Photocatalysis","authors":"Qi Zhang,&nbsp;Jie Wang,&nbsp;Pengju Yang","doi":"10.1021/acs.accounts.6c00568","DOIUrl":"10.1021/acs.accounts.6c00568","url":null,"abstract":"<p>The design of organic photocatalystshas longbeen guided by theassumption that molecular aggregation is detrimental to the performance.This Account presents our laboratory’s systematic developmentof a fundamentally different paradigm, aggregation-induced photocatalysis(AIP). We demonstrate that the noncovalent assembly of molecules canbecome the very source of photocatalytic function, a principle thatoperates in parallel with the well-established paradigm of aggregation-inducedemission (AIE), yet pursues a fundamentally different goal. The centralmechanistic insight, which we term dynamic through-space interactions(DTSI), rests on two synergistic pillars. Through-space orbital interactionsbetween closely packed molecules create delocalized collective electronicstates that dramatically extend light absorption into the red andnear-infrared (NIR) regions. Concurrently, the inherent dynamic behaviorof noncovalent interactions induces asymmetric molecular packing,generating large dipole moments and built-in electric fields thatdrive efficient charge separation.</p><p>We demonstrate the generalityof this framework across three distinctmaterial categories. In π-electron aggregation systems, aggregatesof organic dyes achieve outstanding hydrogen evolution with a quantumyield (QY) reaching 76% at 600 nm, while carbon nitride nanosheetaggregates set a QY of 76.4% at 420 nm. In lone-pair@π-electronaggregation systems, hydrogen-bonded assemblies activate otherwiseforbidden n → π* electronic transition in nonconjugatedsmall molecules, transforming them into visible-light-active photocatalysts.In lone-pair aggregation systems, we challenge the long-held assumptionthat π-conjugation is a prerequisite for semiconductor photocatalysisby demonstrating that nonaromatic biomass such as glucan and chitosangenerates photocatalytic activity solely through through-space electroncouplings of lone-pair electrons.</p><p>A deeper design principleemerges from these studies, which weterm the dynamic order–disorder interactions. Optimal functionarises not from static perfection but from the interplay between thestructural order that enables through-space orbital interactions andthe dynamic disorder that sustains the built-in electric field. ThisAccount provides a unifying framework for understanding and designingaggregate-based photocatalysts with implications that extend fromsolar fuel production to emission phenomena and beyond.</p>","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"59 19","pages":"3256–3266"},"PeriodicalIF":18.0,"publicationDate":"2026-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148985064","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Enantioselective C–H Activations by Metallaelectro-Catalysis","authors":"Sven Erik Peters,&nbsp;Sven Trienes,&nbsp;Yanjun Li,&nbsp;Lutz Ackermann","doi":"10.1021/acs.accounts.6c00509","DOIUrl":"10.1021/acs.accounts.6c00509","url":null,"abstract":"&lt;p&gt;Given the increasing awarenessof the economic and environmentalaspects of chemical syntheses, transformative catalysis platformshave emerged, with molecular electrocatalysis residing at the forefront.It enables sustainable oxidative transformations with high levelsof energy efficiency and resource economy as well as scalability andinherent process safety. Hence, organic electrocatalysis has gainedconsiderable momentum. Further, in terms of sustainable syntheses,the catalyzed activation of otherwise inert C–H bonds was identifiedas a particularly powerful strategy for the rapid assembly of chiralscaffolds, thereby preventing stoichiometric chemical waste. Despiteindisputable advances, these strategies largely relied, until recently,on stoichiometric quantities of often expensive or toxic chemicaloxidants. To this end, metallaelectro-catalysis has emerged as anenabling technology for C–H activations, using the tracelesstransfer of protons and electrons &lt;em&gt;in lieu&lt;/em&gt; of chemicaloxidants, while generating molecular hydrogen as the sole by-product &lt;em&gt;via&lt;/em&gt; the synchronized hydrogen evolution reaction (HER).Although distinct electrooxidative C–H activations were realizedduring the past decade, enantioselective electrochemical catalysishas thus far proven elusive. This Account summarizes our key advancesuntil August 2026 in metallaelectro-catalyzed enantioselective C–Hactivation, streamlining the assembly of chiral molecules featuringvarious stereogenic elements. Thus, palladaelectro-catalyzed C–Halkenylation set the stage for oxidative C–H/C–H couplingstoward atropochiral biaryls, leveraging chiral transient directinggroups (TDGs). Subsequent research efforts have allowed us to broadenthis platform. Since the pronounced complexity of the electrochemicalspace in these systems can complicate discovery and optimization,the implementation of a machine learning (ML) workflow was targeted.This was harnessed for the accelerated optimization of an enantioselectivepalladaelectro-catalyzed annulation reaction. Moreover, the versatilityof rhodium catalysis in enantioselective electrochemical C–Hactivations was mirrored by the e construction of chiral spiropyrazolonesand phthalides. Tailored ruthenium catalysts allowed for the selectivebuildup of atropostable indoles as well as chiral spirocyclic compounds.Taking into consideration the environmental implications and cost-efficacyof transition metal-catalyzed transformations, we further exploredthe utility of earth-abundant transition metals. On this note, enantioselectivecobaltaelectro-catalysis enabled a broad range of highly efficientand enantioselective transformations, such as spirocyclizations, annulationswith alkynes, allenes, and alkenes toward axial-, &lt;em&gt;C&lt;/em&gt;-, and &lt;em&gt;P&lt;/em&gt;-centered chirality, as well as decagram-scalesynthesis realized in flow. The data-driven exploration of newly designedchiral ligands facilitated accelerated discovery in cobaltaelectro-catalyzedC–H activation. Moreover","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"59 19","pages":"3211–3234"},"PeriodicalIF":18.0,"publicationDate":"2026-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149022342","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"C-Glycosylation as the Organizing Principle for Heterocycle Construction and Tailoring in C-Nucleosides Biosynthesis","authors":"Daan Ren,&nbsp;Yu-Hsuan Lee,&nbsp;Hung-wen Liu","doi":"10.1021/acs.accounts.6c00352","DOIUrl":"10.1021/acs.accounts.6c00352","url":null,"abstract":"<p><em>C</em>-Nucleosides,characterizedby a chemically robustC–C glycosidic bond in place of the canonical C–N linkage,represent a distinct class of nucleoside natural products with diversebiological activities. Their close structural similarity to <em>N</em>-nucleosides enables their incorporation into primary metabolicprocesses, including de novo nucleoside biosynthesis and RNA polymerization.As a result, both natural and synthetic <em>C</em>-nucleosidesexhibit potent antibacterial, antiviral, and anticancer activities,making them attractive targets for drug development in medicinal chemistryand chemical biology. Natural product discovery efforts have uncovereda number of <em>C</em>-nucleosides in which C–C glycosidicbond formation generally involves either decarboxylative electrophilicaromatic substitution or Knoevenagel-Mannich condensation. In bothcases, <em>C</em>-glycosylation relies on the biosynthesisof highly nucleophilic heterocycles prior to glycosidic bond formation.These nucleophiles arise from distinct precursors, including <span>d</span>-glutamate-derived heterocyclic carboxylates and <span>l</span>-glutamine-derivedscaffolds formed via oxidative cyclization. Following <em>C</em>-glycosylation, <span>d</span>-glutamate-derived intermediates undergopyrimidine elaboration that parallels aminopyrimidine formation inde novo purine biosynthesis, whereas <span>l</span>-glutamine-derivedheterocycles undergo oxidative tailoring reactions that ultimatelydefine their final structure and biological function. Thus, <em>C</em>-glycosylation is indeed the central mechanistic featureof <em>C</em>-nucleoside biosynthesis that places requirementson the initial construction of the nucleophilic heterocycle to facilitateC–C bond formation and in the process defines the propertiesthat govern subsequent tailoring reactions.</p>","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"59 19","pages":"3036–3049"},"PeriodicalIF":18.0,"publicationDate":"2026-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148894890","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}