Accounts of Chemical Research最新文献

{"title":"Nonconjugated Polyesters Emitting Full-Color Clusteroluminescence","authors":"Bo Chu, Haoke Zhang, Xinghong Zhang, Ben Zhong Tang","doi":"10.1021/acs.accounts.5c00251","DOIUrl":"https://doi.org/10.1021/acs.accounts.5c00251","url":null,"abstract":"Photoluminescent polymers have been attracting great attention, owing to their intrinsic mechanical properties, diverse structures, and the ability of intra/inter-chain interactions to regulate their luminescent properties. Conventional luminescent polymers contain classical luminophores, such as extended π-conjugated aromatic carbocyclic and heterocyclic groups, which could emit multicolor photoluminescence (PL) but suffer from biotoxicity, poor processability, complicated synthesis, and environmental hazards. In recent decades, heteroatom (e.g., O, N)-rich nonconjugated polymers without classical luminophores have been revealed to exhibit abnormal photoluminescence, namely, clusteroluminescence (CL), originating from through-space electronic interaction between heteroatomic groups. These newly discovered heteroatomic polymers take advantage of low cost, mass production, processability, and biocompatibility. Therefore, developing full-color CL polymers and revealing their unique PL mechanisms are highly desired in chemistry, biology, and material science.","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"250 1","pages":""},"PeriodicalIF":18.3,"publicationDate":"2025-06-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144237214","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":"Nonconjugated Polyesters Emitting Full-Color Clusteroluminescence","authors":"Bo Chu,&nbsp;Haoke Zhang*,&nbsp;Xinghong Zhang* and Ben Zhong Tang,&nbsp;","doi":"10.1021/acs.accounts.5c0025110.1021/acs.accounts.5c00251","DOIUrl":"https://doi.org/10.1021/acs.accounts.5c00251https://doi.org/10.1021/acs.accounts.5c00251","url":null,"abstract":"<p >Photoluminescent polymers have been attracting great attention, owing to their intrinsic mechanical properties, diverse structures, and the ability of intra/inter-chain interactions to regulate their luminescent properties. Conventional luminescent polymers contain classical luminophores, such as extended π-conjugated aromatic carbocyclic and heterocyclic groups, which could emit multicolor photoluminescence (PL) but suffer from biotoxicity, poor processability, complicated synthesis, and environmental hazards. In recent decades, heteroatom (e.g., O, N)-rich nonconjugated polymers without classical luminophores have been revealed to exhibit abnormal photoluminescence, namely, clusteroluminescence (CL), originating from through-space electronic interaction between heteroatomic groups. These newly discovered heteroatomic polymers take advantage of low cost, mass production, processability, and biocompatibility. Therefore, developing full-color CL polymers and revealing their unique PL mechanisms are highly desired in chemistry, biology, and material science.</p><p >In this Account, we summarize our research on nonconjugated polyester for high-efficiency full-color CL via structure-driven through-space (<i>n</i>, π*) interaction (TSI-(<i>n</i>, π*)), as a new paradigm for designing nonconjugated CL polymers with deeper insight into CL, including the molecular design of polyesters, the structure–luminescence relationship, and mechanism. This Account starts with a brief introduction to the recent development of CL in heteroatom-rich polymers as well as polyesters containing <i>n</i> and π electrons as one of the classical CL polymers. Then, we discuss the synthetic methods of polyesters based on the polymerization-induced emission (PIE) strategy, transforming nonluminescent monomer into luminescent polyester, or achieving red shifts in the emission wavelength through multiple through-space electronic interactions from polymer hierarchical structures. The third part summarizes the regulation of CL properties (wavelength and efficiency) by altering TSI-(<i>n</i>, π*) relying on hierarchical structures (segmental structures, conformation, end-group structures, and electronic bridge structures) of polyesters, achieving high-efficiency full-color CL (400–800 nm) from blue to near-infrared (NIR). We then proposed subnanometer TSI-(<i>n</i>, π*) and photomodulated through-space electronic coupling in polyesters for CL mechanism and provided an outlook on the development of CL polyester materials and applications.</p>","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"58 12","pages":"1924–1935 1924–1935"},"PeriodicalIF":16.4,"publicationDate":"2025-06-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144296757","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":"On the Coordination Environment of Single-Atom Catalysts","authors":"Leilei Zhang,&nbsp;Xiaofeng Yang,&nbsp;Jian Lin,&nbsp;Xuning Li,&nbsp;Xiaoyan Liu,&nbsp;Botao Qiao,&nbsp;Aiqin Wang* and Tao Zhang*,&nbsp;","doi":"10.1021/acs.accounts.5c0014010.1021/acs.accounts.5c00140","DOIUrl":"https://doi.org/10.1021/acs.accounts.5c00140https://doi.org/10.1021/acs.accounts.5c00140","url":null,"abstract":"<p >Single-atom catalysis has become one of the most active frontiers in catalysis in the past decade. This concept not only gives birth to a new kind of heterogeneous catalysts featuring well-defined isolated active sites and strong covalent (or electronic) metal–support interaction, which deliver unique catalytic activity, selectivity, and stability distinct from their nanoparticulate counterparts, but also together with the principles and concepts in history, reshapes our understanding of heterogeneous catalysis and drives the catalysis research from the nanoscale and subnanoscale to the more precise atomic scale.</p><p >Due to the extremely high free energy, the isolated gaseous metal atoms cannot survive alone but are stabilized on the support materials through strong chemical binding, forming metal-centered coordination moieties resembling organometallics in homogeneous catalysis. The coordination environment, including the inner shell and outer shell comprised of the support, reactants, and environmental molecules, determines the electronic and geometric properties of central atoms and, in turn, the catalytic performance of SACs. In some cases, the neighboring atoms on the support can be directly involved in the catalysis in a metal-support concerted catalysis manner. Therefore, the coordination environment not only serves as an effective descriptor of the structure–performance relationship but also provides great opportunities to fabricate better-performed SACs through modulation of the coordination atoms, number, promoter, and so on.</p><p >In this Account, recent advances in our group in the identification and modulation of the coordination environment of SACs are highlighted. First, the heterogeneity of the coordination environment of SACs is discussed regarding the nonuniform structure and composition of the support. Then, various approaches to tune the inner-shell and outer-shell coordination environments are shown for the effective improvement of the catalytic performance of SACs. Finally, the structure evolution of SACs driven by external stimuli and reactant/products is discussed. The atomic understanding of the coordination environment of SACs will help to elucidate the nature of single-atom catalysis and enrich the theoretical aspects of heterogeneous catalysis.</p>","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"58 12","pages":"1878–1892 1878–1892"},"PeriodicalIF":16.4,"publicationDate":"2025-06-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144296535","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":"On the Coordination Environment of Single-Atom Catalysts","authors":"Leilei Zhang, Xiaofeng Yang, Jian Lin, Xuning Li, Xiaoyan Liu, Botao Qiao, Aiqin Wang, Tao Zhang","doi":"10.1021/acs.accounts.5c00140","DOIUrl":"https://doi.org/10.1021/acs.accounts.5c00140","url":null,"abstract":"Single-atom catalysis has become one of the most active frontiers in catalysis in the past decade. This concept not only gives birth to a new kind of heterogeneous catalysts featuring well-defined isolated active sites and strong covalent (or electronic) metal–support interaction, which deliver unique catalytic activity, selectivity, and stability distinct from their nanoparticulate counterparts, but also together with the principles and concepts in history, reshapes our understanding of heterogeneous catalysis and drives the catalysis research from the nanoscale and subnanoscale to the more precise atomic scale.","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"14 1","pages":""},"PeriodicalIF":18.3,"publicationDate":"2025-06-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144237215","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":"","authors":"Erin E. Carlson*,&nbsp;Nicholas Sparks and Shivani Diwakar,&nbsp;","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"58 11","pages":"XXX-XXX XXX-XXX"},"PeriodicalIF":16.4,"publicationDate":"2025-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.accounts.5c00113","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144427721","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":"What is Editing?","authors":"Mark D. Levin*,&nbsp;Richmond Sarpong and Alison E. Wendlandt,&nbsp;","doi":"10.1021/acs.accounts.5c0026810.1021/acs.accounts.5c00268","DOIUrl":"https://doi.org/10.1021/acs.accounts.5c00268https://doi.org/10.1021/acs.accounts.5c00268","url":null,"abstract":"","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"58 11","pages":"1725–1726 1725–1726"},"PeriodicalIF":16.4,"publicationDate":"2025-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144194081","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":"","authors":"Zhengkai Tu,&nbsp;Sourabh J. Choure,&nbsp;Mun Hong Fong,&nbsp;Jihye Roh,&nbsp;Itai Levin,&nbsp;Kevin Yu,&nbsp;Joonyoung F. Joung,&nbsp;Nathan Morgan,&nbsp;Shih-Cheng Li,&nbsp;Xiaoqi Sun,&nbsp;Huiqian Lin,&nbsp;Mark Murnin,&nbsp;Jordan P. Liles,&nbsp;Thomas J. Struble,&nbsp;Michael E. Fortunato,&nbsp;Mengjie Liu,&nbsp;William H. Green,&nbsp;Klavs F. Jensen and Connor W. Coley*,&nbsp;","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"58 11","pages":"XXX-XXX XXX-XXX"},"PeriodicalIF":16.4,"publicationDate":"2025-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.accounts.5c00155","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144427685","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":"","authors":"Carole Daiguebonne,&nbsp;Chloé Blais,&nbsp;Kevin Bernot and Olivier Guillou*,&nbsp;","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"58 11","pages":"XXX-XXX XXX-XXX"},"PeriodicalIF":16.4,"publicationDate":"2025-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.accounts.5c00190","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144427686","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":"Catalytic 1,2-Radical Acyloxy Migration: A Strategy to Access Novel Chemical Space and Reaction Profiles.","authors":"Gaoyuan Zhao, Upasana Mukherjee, Wang Yao, Ming-Yu Ngai","doi":"10.1021/acs.accounts.5c00205","DOIUrl":"10.1021/acs.accounts.5c00205","url":null,"abstract":"<p><p>ConspectusRadical migration represents a powerful strategy for reaction discovery and development in organic synthesis, offering access to unprecedented functional molecules and chemical space. In this Account, we describe our contributions to the field, particularly focusing on 1,2-radical acyloxy migration (RAM), a process involving the transposition of a radical and an acyloxy group. We highlight its application in carbohydrate modification and allyl carboxylate trifunctionalization, demonstrating how this reactivity enables the streamlined synthesis of novel glycomimetics and facilitates selective 1,2,3-trifunctionalization of allyl carboxylates. These advances establish 1,2-RAM as a versatile platform for catalytic radical transformations, unlocking new opportunities in reaction development and functional molecule design.Our approach leverages excited-state palladium and ground-state nickel catalysis to modify carbohydrates, specifically at the C2 position. This strategy enables C2-deoxy-hydrogenation, deuteration, iodination, alkenylation, allylation, ketonylation, and arylation reactions, providing direct access to unprecedented glycomimetics. These transformations streamline the synthesis of structurally diverse glycomimetics, facilitating the discovery and development of carbohydrate-based functional molecules. Furthermore, the mild reaction conditions and high functional group tolerance of these catalytic systems make them particularly attractive for late-stage functionalization, broadening their applicability in complex molecule synthesis.Beyond carbohydrates, we have extended 1,2-RAM reactivity to achieve unprecedented 1,2,3-trifunctionalization of allyl carboxylates. By employing excited-state phosphine catalysis, we demonstrate a 1,3-carbobromination reaction accompanied by an acyloxy shift. This proof-of-concept study lays the foundation for developing a broader range of 1,2,3-trifunctionalization reactions, effectively transforming allyl carboxylates into substituted isopropyl carboxylate donors. This advancement expands the synthetic utility of allyl carboxylates, enabling the rapid construction of structurally diverse molecular scaffolds.In summary, the 1,2-RAM reactivity opens a new avenue for reaction discovery and development, granting access to new functional molecules and chemical space. The mild conditions, broad functional group compatibility, and unique reactivity of this approach make it a valuable tool for chemical synthesis. We anticipate that merging 1,2-RAM with other catalytic platforms will further advance bond disconnection strategies, provide access to new functional molecules, and expand the frontiers of chemical synthesis.</p>","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":" ","pages":"1815-1829"},"PeriodicalIF":16.4,"publicationDate":"2025-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144118326","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":"Multiphase Electrochemiluminescence of Microdroplets and Radical Salts","authors":"Brady R. Layman,&nbsp;Daniel M. Carrel and Jeffrey E. Dick*,&nbsp;","doi":"10.1021/acs.accounts.5c0013510.1021/acs.accounts.5c00135","DOIUrl":"https://doi.org/10.1021/acs.accounts.5c00135https://doi.org/10.1021/acs.accounts.5c00135","url":null,"abstract":"&lt;p &gt;Over the past decade, experiments involving microdroplets have challenged the framework of chemistry. These droplets constitute a multiphase system, where the dynamic interplay between solid, liquid, and gas influences reactions. Multiphase systems are prevalent in nature and possess unique physicochemical properties. However, in chemistry, phase boundary reactivity is often overlooked because molecules experience “bulk” reactivity. These systems are prevalent in biological processes, such as cell mitosis, biological sensor technology, organic synthesis, and pollution remediation.&lt;/p&gt;&lt;p &gt;Recently, our group has developed different strategies of electrochemiluminescence (also called electrogenerated chemiluminescence, both shortened to ECL) microscopy and imaging to understand the unique properties and dynamics at electrified interfaces. ECL takes advantage of the reactivity between a luminophore that radically annihilates with a strong oxidizing or reducing reagent. If the enthalpy of annihilation is high enough, the luminophore will be left in an excited state and radiatively decay, producing light. Thus, ECL requires no incident light, and ECL microscopy has unique analytical figures of merit due to the light being emitted close to the electrified interface (1–10 μm), providing insight into reactivity within the electrode’s proximity.&lt;/p&gt;&lt;p &gt;This Account will detail our group’s efforts in discovering ECL reactions in environments exhibiting native triphasic (liquid|liquid|electrode) interfaces and reactions where new phases are formed (e.g., bubble nucleation and electroprecipitation). We first began developing the tools necessary to image liquid|liquid interfaces and discovered that, when neighboring droplets fuse together, small pockets (inclusions) of the continuous phase existed inside the merged droplets. Studies of inclusion chemical reactivity have led to the interesting observation that small droplets on electrified interfaces can act as gas micropumps, protecting the electrode from gas buildup during electrocatalytic reactions.&lt;/p&gt;&lt;p &gt;Even though a strength of ECL is that emission is confined directly to the surface, this can also be a significant weakness, considering interesting chemical phenomena can occur far away from the electrode surface. One recent thrust in the community is discovering new ways of using ECL far away from the electrode surface, a phenomenon termed “Through-Space ECL”. Our group has used this technique to measure bubble forces at phase boundaries far from the electrode surface.&lt;/p&gt;&lt;p &gt;By playing on the relative solubilities of ECL reactants and products, we showed that, if a radical ion can be generated and precipitates more quickly than its radical lifetime, radical salts can be formed. These radical salts are a way to fossilize highly energetic molecules. We have used this seemingly new chemical tenet to effectively bottle up ECL, fossilizing the reactants to be used elsewhere in space and time. Given our","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"58 12","pages":"1856–1866 1856–1866"},"PeriodicalIF":16.4,"publicationDate":"2025-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144296383","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}