{"title":"Correction to “Steric and Electronic Influence of Excited-State Decay in Cu(I) MLCT Chromophores”","authors":"Felix N. Castellano, Michael C. Rosko","doi":"10.1021/acs.accounts.4c00720","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00720","url":null,"abstract":"The slope presented in Figure 11 illustrates a compelling linear correlation over an emission energy range of ∼0.4 eV (∼3200 cm<sup>–1</sup>) having a slope of −11.3 natural log units/eV, illustrating that energy gap considerations majorly influence excited state decay in this class of chromophores in the absence of donor solvent interactions, regardless of alkyl substitution pattern.<img alt=\"\" src=\"/cms/10.1021/acs.accounts.4c00720/asset/images/medium/ar4c00720_0001.gif\"/> This article has not yet been cited by other publications.","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":null,"pages":null},"PeriodicalIF":18.3,"publicationDate":"2024-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142598514","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":"Origin of the Difference in Proton Transport Direction between Inward and Outward Proton-Pumping Rhodopsins","authors":"Taito Urui, Yasuhisa Mizutani","doi":"10.1021/acs.accounts.4c00488","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00488","url":null,"abstract":"Active transport is a vital and ubiquitous process in biological phenomena. Ion-pumping rhodopsins are light-driven active ion transporters that share a heptahelical transmembrane structural scaffold in which the all-<i>trans</i> retinal chromophore is covalently bonded through a Schiff base to a conserved lysine residue in the seventh transmembrane helix. Bacteriorhodopsin from <i>Halobacterium salinarum</i> was the first ion-pumping rhodopsin to be discovered and was identified as an outward proton-pumping rhodopsin. Since the discovery of bacteriorhodopsin in 1971, many more ion-pumping rhodopsins have been isolated from diverse microorganisms spanning three domains (bacteria, archaea, and eukaryotes) and giant viruses. In addition to proton-pumping rhodopsins, chloride ion- and sodium ion-pumping rhodopsins have also been discovered. Furthermore, diversity of ion-pumping rhodopsins was found in the direction of ion transport; i.e., rhodopsins that pump protons <i>inward</i> have recently been discovered. Very intriguingly, the inward proton-pumping rhodopsins share structural features and many conserved key residues with the outward proton-pumping rhodopsins. However, a central question remains unchanged despite the increasing variety: how and why do the ion-pumping rhodopsins undergo interlocking conformational changes that allow unidirectional ion transfer within proteins? In this regard, it is an effective strategy to compare the structures and their evolutions in the proton-pumping processes of both inward and outward proton-pumping rhodopsins because the comparison sheds light on key elements for the unidirectional proton transport. We elucidated the proton-pumping mechanism of the inward and outward proton-pumping rhodopsins by time-resolved resonance Raman spectroscopy, a powerful technique for tracking the structural evolutions of proteins at work that are otherwise inaccessible.","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":null,"pages":null},"PeriodicalIF":18.3,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142594516","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}
Shiyi Yang, Tongliang Zhou, Xiang Yu, Steven P Nolan, Michal Szostak
{"title":"[Pd(NHC)(μ-Cl)Cl]<sub>2</sub>: The Highly Reactive Air- and Moisture-Stable, Well-Defined Pd(II)-N-Heterocyclic Carbene (NHC) Complexes for Cross-Coupling Reactions.","authors":"Shiyi Yang, Tongliang Zhou, Xiang Yu, Steven P Nolan, Michal Szostak","doi":"10.1021/acs.accounts.4c00549","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00549","url":null,"abstract":"<p><p>ConspectusPalladium-catalyzed cross-coupling reactions owing to their high specificity and superb chemoselectivity represent a powerful tool for the rapid construction of C-C and C-X bonds across various areas of chemical research, including pharmaceutical development, polymer and agrochemical industries, bioactive natural products, and advanced functional materials, rendering them indispensable for modern synthetic chemists. The major driving force for the advances in this critical field is the design of increasingly more reactive and more selective ligands and precatalysts that aim not only to address challenging cross-coupling processes but also to achieve optimal reactivity, selectivity, and functional group compatibility under mild, user-friendly, operationally simple, and broadly applicable conditions. In this context, Pd(II)-N-heterocyclic carbene complexes (NHC = N-heterocyclic carbene) have garnered prevalent attention among practitioners of organic synthesis due to their unique electronic and steric characteristics that are unmatched among other ligands. In particular, the superior σ-donating ability of NHC ligands in conjunction with conformational flexibility as well as the ease of steric and electronic modification and high stability to air and moisture enable highly effective fundamental elementary steps in catalytic cycles and facile formation of well-defined complexes.The key factor in the design of well-defined, air- and moisture-stable Pd(II) precatalysts involves the incorporation of supporting ligands, which are essential for ensuring the stability of Pd(II)-NHC complexes and facile activation of Pd(II)-NHC precatalysts to catalytically active monoligated Pd(0)-NHC species under the reaction conditions. Notably, [Pd(NHC)(μ-Cl)Cl]<sub>2</sub> chloro dimers, which can be readily synthesized via a one-pot, atom-economic process, are the most reactive Pd(II)-NHC complexes synthesized to date. These well-defined, air- and moisture-stable dimers readily dissociate to monomers and are activated to Pd(0)-NHC catalysts under both mild and strong base conditions, showcasing enhanced reactivity and selectivity among their Pd(II)-NHC counterparts. This balance between high, operationally simple stability, which is characteristic of Pd(II) complexes together with the ease of activation to the strongly nucleophilic Pd(0)-NHC catalysts, renders [Pd(NHC)(μ-Cl)Cl]<sub>2</sub> the most reactive Pd(II)-NHC precatalysts developed to date for a broad range of general cross-coupling processes, including C-X, C-O, C-N, and C-S activation and enabling the direct late-stage functionalization of complex compounds decorated with a wide range of sensitive functional groups.In this Account, we outline [Pd(NHC)(μ-Cl)Cl]<sub>2</sub> as a highly reactive Pd(II)-NHC precatalyst that should be routinely used as the first choice Pd complexes for a wide range of challenging cross-coupling reactions. The advancements in this field over the past 20 years emp","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":null,"pages":null},"PeriodicalIF":16.4,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142589538","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}
Rotem Edri, Loren Dean Williams, Moran Frenkel-Pinter
{"title":"From Catalysis of Evolution to Evolution of Catalysis.","authors":"Rotem Edri, Loren Dean Williams, Moran Frenkel-Pinter","doi":"10.1021/acs.accounts.4c00196","DOIUrl":"10.1021/acs.accounts.4c00196","url":null,"abstract":"<p><p>ConspectusThe mystery of the origins of life is one of the most difficult yet intriguing challenges to which humanity has grappled. How did biopolymers emerge in the absence of enzymes (evolved biocatalysts), and how did long-lasting chemical evolution find a path to the highly selective complex biology that we observe today? In this paper, we discuss a chemical framework that explores the very roots of catalysis, demonstrating how standard catalytic activity based on chemical and physical principles can evolve into complex machineries. We provide several examples of how prebiotic catalysis by small molecules can be exploited to facilitate polymerization, which in biology has transformed the nature of catalysis. Thus, catalysis evolved, and evolution was catalyzed, during the transformation of prebiotic chemistry to biochemistry. Traditionally, a catalyst is defined as a substance that (i) speeds up a chemical reaction by lowering activation energy through different chemical mechanisms and (ii) is not consumed during the course of the reaction. However, considering prebiotic chemistry, which involved a highly diverse chemical space (i.e., high number of potential reactants and products) and constantly changing environment that lacked highly sophisticated catalytic machinery, we stress here that a more primitive, broader definition should be considered. Here, we consider a catalyst as any chemical species that lowers activation energy. We further discuss various demonstrations of how simple prebiotic molecules such as hydroxy acids and mercaptoacids promote the formation of peptide bonds via energetically favored exchange reactions. Even though the small molecules are partially regenerated and partially retained within the resulting oligomers, these prebiotic catalysts fulfill their primary role. Catalysis by metal ions and in complex chemical mixtures is also highlighted. We underline how chemical evolution is primarily dictated by kinetics rather than thermodynamics and demonstrate a novel concept to support this notion. Moreover, we propose a new perspective on the role of water in prebiotic catalysis. The role of water as simply a \"medium\" obscures its importance as an active participant in the chemistry of life, specifically as a very efficient catalyst and as a participant in many chemical transformations. Here we highlight the unusual contribution of water to increasing complexification over the course of chemical evolution. We discuss possible pathways by which prebiotic catalysis promoted chemical selection and complexification. Taken together, this Account draws a connection line between prebiotic catalysis and contemporary biocatalysis and demonstrates that the fundamental elements of chemical catalysis are embedded within today's biocatalysts. This Account illustrates how the evolution of catalysis was intertwined with chemical evolution from the very beginning.</p>","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":null,"pages":null},"PeriodicalIF":16.4,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11542150/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142379420","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Two-Dimensional Covalent Organic Frameworks: Structural Insights across Different Length Scales and Their Impact on Photocatalytic Efficiency.","authors":"Islam E Khalil, Prasenjit Das, Arne Thomas","doi":"10.1021/acs.accounts.4c00491","DOIUrl":"10.1021/acs.accounts.4c00491","url":null,"abstract":"<p><p>ConspectusCovalent organic frameworks (COFs) are a rapidly emerging class of crystalline porous polymers, characterized by their highly defined, predictable, and tunable structure, porosity, and properties. COFs can form both two-dimensional (2D) and three-dimensional (3D) architectures, each with unique characteristics and potential applications. 2D COFs have attracted particular interest due to their favorable structural and optoelectronic properties. They can be equipped with a range of different functional moieties in their backbone, ranging from acidic to basic, from hydrophilic to hydrophobic, and from metal-coordinating to redox-active functions. In addition, their crystallinity, high specific surface area, and remarkable thermal and chemical stability make them attractive for a variety of applications, including gas separation, catalysis, energy storage, and optoelectronics.This Account provides a detailed overview of our recent efforts to synthesize and apply 2D COFs. First, various synthesis routes are discussed, focusing on methods that involve reversible and irreversible linkage reactions. Reversible reactions, such as imine or boronate ester formation, are advantageous for producing highly crystalline COFs because they allow for error correction during synthesis. In contrast, irreversible reactions, such as carbon-carbon or carbon-nitrogen bond formation, yield COFs with greater chemical stability, although controlling crystallinity can be more challenging. Our group has contributed significantly to refining these methods to balance crystallinity and stability, enhancing the performance of the resulting 2D COFs.In addition to different binding patterns, we have also developed strategies to control the micro- and macromorphologies of COFs, which is crucial for optimizing their properties for specific applications. For example, we have explored the synthesis of hierarchical porous COFs by using templating techniques or by forming composites with other functional materials. These strategies enable us to fine-tune the porosity and surface properties of COFs, thereby improving their performance in applications like catalysis. Hierarchical structures in particular enhance photocatalytic efficiency by providing a larger surface area for light absorption and facilitating the transport of photogenerated charge carriers.We further examine the practical applications of 2D COFs, with a primary focus on photocatalysis. Photocatalysis uses light to enable or accelerate chemical reactions, and 2D COFs are ideal for this purpose due to their tunable band gaps and large surface areas. Our research has shown that 2D COFs are highly versatile photocatalysts that can effectively catalyze reactions such as water splitting, carbon dioxide reduction, hydrogen peroxide formation, and cross-coupling reactions. By exploiting the unique properties of 2D COFs, we have achieved significant improvement in many photocatalytic reactions.With this comprehensiv","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":null,"pages":null},"PeriodicalIF":16.4,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11542146/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142453179","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Challenges and Opportunities in 2D Materials","authors":"Christopher E. Shuck*, Xu Xiao and Zhiyong Wang, ","doi":"10.1021/acs.accounts.4c0062510.1021/acs.accounts.4c00625","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00625https://doi.org/10.1021/acs.accounts.4c00625","url":null,"abstract":"","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":null,"pages":null},"PeriodicalIF":16.4,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142577528","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":"Challenges and Opportunities in 2D Materials.","authors":"Christopher E Shuck, Xu Xiao, Zhiyong Wang","doi":"10.1021/acs.accounts.4c00625","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00625","url":null,"abstract":"","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":null,"pages":null},"PeriodicalIF":16.4,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142574813","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":"Sequential Linker Installation in Metal-Organic Frameworks.","authors":"Zongsu Han, Yihao Yang, Joshua Rushlow, Rong-Ran Liang, Hong-Cai Zhou","doi":"10.1021/acs.accounts.4c00564","DOIUrl":"10.1021/acs.accounts.4c00564","url":null,"abstract":"<p><p>ConspectusMetal-organic frameworks (MOFs) represent a sophisticated blend of inorganic and organic components, promoting the development of coordination chemistry greatly and offering a versatile platform for tailored functionalities. By combining various metal nodes, organic linkers, and functional guests, MOFs provide numerous pathways for their design, synthesis, and customization. Among these, sequential linker installation (SLI) stands out as a novel and crucial strategy, enabling the precise integration of desired properties and functions at the atomic scale. SLI enhances structural diversity and stability while facilitating the meticulous construction of robust frameworks by leveraging open metal sites and functional organic linkers at targeted locations. Compared to the direct synthesis of MOFs, postsynthetic modification methods allow for precise regulation of their structures and corresponding properties. While unlike conventional postsynthetic modification methods, SLI requires the careful selection of linkers and framework design to ensure precise positioning for installation, which gives rise to the well-designed and ordered positions for the installed linkers, confirmed directly by X-ray diffraction technology.Recent advancements in MOF synthesis have led to the creation of increasingly tailored flexible matrix structures, particularly due to the diverse connection modes of multicore metal clusters, especially for the Zr<sub>6</sub> cluster. The spatial hindrance of certain ligands has resulted in the formation of unsaturated metal clusters and various missing linker pockets. Examples of these advanced MOFs include PCN-606, PCN-608, PCN-609, PCN-700, and PCN-808, which feature specific open metal sites and certain framework flexibility conducive to SLI. Strategically positioned open metal sites within these frameworks serve as predetermined anchor points for desired functional molecules, while the frameworks' flexibility can accommodate molecules of varying sizes to a certain extent, enlarging the scopes of application greatly. This precise positioning of functional groups enables the creation of tailored sites for enhanced applications, such as adsorption, catalysis, and recognition.In this Account, we delve into the intricate process of designing and synthesizing MOFs with appropriate missing-linker pockets for the aforementioned applications. We discuss the meticulous selection of functional linkers and the methods used to insert them into the corresponding missing-linker pockets within the MOFs. Additionally, we explore the diverse properties and functionalities of the resulting MOFs, focusing on their adsorptive, catalytic, and recognition performance. Furthermore, we provide insights into the future trajectory of SLI methods, complemented by our recent works. This Account not only reviews the evolution of the SLI method but also underscores its practical applications across various functional domains, paving a rational p","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":null,"pages":null},"PeriodicalIF":16.4,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11542145/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142453180","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Sanha Park, Kunwoo Lee, Sudakar Padmanaban, Yunho Lee
{"title":"Small Molecule Activation at the <sup>acri</sup>PNP Pincer-Supported Nickel Sites.","authors":"Sanha Park, Kunwoo Lee, Sudakar Padmanaban, Yunho Lee","doi":"10.1021/acs.accounts.4c00401","DOIUrl":"10.1021/acs.accounts.4c00401","url":null,"abstract":"<p><p>ConspectusNickel pincer systems have recently attracted much attention for applications in various organometallic reactions and catalysis involving small molecule activation. Their exploration is in part motivated by the presence of nickel in natural systems for efficient catalysis. Among such systems, the nickel-containing metalloenzyme carbon monoxide dehydrogenase (CODH) efficiently and reversibly converts CO<sub>2</sub> to CO at its active site. The generated CO moves through a channel from the CODH active site and is transported to a dinuclear nickel site of acetyl-coenzyme A synthase (ACS), which catalyzes organometallic C-S and C-C bond forming reactions. An analogous C-S bond activation process is also mediated by the nickel containing enzyme methyl-coenzyme M reductase (MCR). The nickel centers in these systems feature sulfur- and nitrogen-rich environments, and in the particular case of lactate racemase, an organometallic nickel pincer motif revealing a Ni-C bond is observed. These bioinorganic systems inspired the development of several nickel pincer scaffolds not only to mimic enzyme active sites and their reactivity but also to further extend low-valent organonickel chemistry. In this <i>Account</i>, we detail our continuing efforts in the chemistry of nickel complexes supported by acridane-based PNP pincer ligands focusing on our long-standing interest in biomimetic small molecule activation. We have employed a series of diphosphinoamide pincer ligands to prepare various nickel(II/I/0) complexes and to study the conversion of C<sub>1</sub> chemicals such as CO and CO<sub>2</sub> to value-added products. In the transformation of C<sub>1</sub> chemicals, the key C-O bond cleavage and C-E bond (E = C, N, O, or S, etc.) formation steps typically require overcoming high activation barriers. Interestingly, enzymatic systems overcome such difficulties for C<sub>1</sub> conversion and operate efficiently under ambient conditions with the use of nickel organometallic chemistry. Furthermore, we have extended our efforts to the conversion of NO<sub><i>x</i></sub> anions to NO via the sequential deoxygenation by nickel mediated carbonylation, which was applied to catalytic C-N coupling to produce industrially important organonitrogen compound oximes as a strategy for NO<sub><i>x</i></sub> conversion and utilization (NCU). Notably, the rigidified <sup>acri</sup>PNP pincer backbone that enforces a planar geometry at nickel was found to be an important factor for diversifying organometallic transformations including (a) homolysis of various σ-bonds mediated by T-shaped nickel(I) metalloradical species, (b) C-H bond activation mediated by a nickel(0) dinitrogen species, (c) selective CO<sub>2</sub> reactivity of nickel(0)-CO species, (d) C-C bond formation at low-valent nickel(I or 0)-CO sites with iodoalkanes, and (e) catalytic deoxygenation of NO<sub><i>x</i></sub> anions and subsequent C-N coupling of a nickel-NO species with alkyl halides","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":null,"pages":null},"PeriodicalIF":16.4,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142379369","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":"Photocatalysis with Covalent Organic Frameworks.","authors":"Yongzhi Chen, Donglin Jiang","doi":"10.1021/acs.accounts.4c00517","DOIUrl":"10.1021/acs.accounts.4c00517","url":null,"abstract":"<p><p>ConspectusUtilizing light to enable chemical conversions presents a green and sustainable approach to produce fuels and chemicals, and photocatalysis is one of the key chemical technologies that needs to be well developed in this century. Despite continuous progress in the advancement of various photocatalysts based on small inorganic and organic compounds, polymers, and networks, designing and constructing photocatalysts that combine activity, selectivity, and reusability remains a challenging goal. For catalytic activity, the difficulty originates from the complexity of photochemical reactions, where the light-harvesting system, multielectron and multihole-involving processes, and pinpoint mass delivery simultaneously need to be established in the system. For selectivity, the difficulty stems from the elaborate design of catalytic sites and space, especially their orbital energy levels, spatial arrangement, and environment; developing a molecular strategy that enables an overall design and control of these factors of different aspects is necessary yet arduous. For reusability, the difficulty arises from the stability and recyclability of the photocatalysts upon continuous operation under photoredox reaction conditions. How to recover photocatalysts in an energy-saving way to enable their cyclic use while retaining activity and selectivity is at the core of this problem. These bottleneck issues reflect that molecular design of a photocatalyst is not a simple summation of the above requirements, but a systematic scheme that can organically interlock various aspects is needed.To enable such an elaborate design and precise control, a basic requirement of the scaffold for constructing a promising photocatalyst is that its primary and high-order structures should be molecularly predesignable and synthetically controllable. Such a molecular regime has successfully evolved in natural photosynthesis, where light-harvesting chlorophyll antennae and photocatalytic centers are spatially well-organized and energetically well-defined to build ways for exciton migration, photoinduced electron transfer and charge separation, electron and hole flows, and oxidation of water and reduction of carbon dioxide, thereby converting water into oxygen to release ATP and NADPH via the light reaction and carbon dioxide into glucose with ATP and NADPH through the dark reaction. Similarly, a predesignable polymeric scaffold would be promising for integrating these complex photochemical processes to construct photocatalysts.Covalent organic frameworks (COFs) are a class of extended yet polymeric materials that enable the organization of organic units or metallo-organic moieties into well-defined architectures. In principle, COFs are molecularly designable with topology diagrams and synthetically controllable through polymerization reactions, offering an irreplaceable platform for designing and synthesizing photocatalysts. This feature enticed researchers to develop vari","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":null,"pages":null},"PeriodicalIF":16.4,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142379419","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}