Accounts of Chemical Research最新文献

{"title":"Synthesis of Axially Chiral Compounds via Transition Metal-Catalyzed Atroposelective C-H Functionalization.","authors":"Gang Liao, Bing-Feng Shi","doi":"10.1021/acs.accounts.5c00173","DOIUrl":"https://doi.org/10.1021/acs.accounts.5c00173","url":null,"abstract":"<p><p>ConspectusAxially chiral skeletons are prevalent in natural products and biologically important compounds, and they are widely utilized as privileged scaffolds in enantioselective catalysis. Consequently, the catalytic atroposelective synthesis of enantiopure atropisomers has garnered considerable attention. A variety of synthetic strategies involving metal catalysis or organocatalysis have been developed. Among these elegant approaches, transition metal-catalyzed enantioselective C-H activation has emerged as an atom- and step-economical strategy to streamline the construction of axially chiral compounds in recent years.In this Account, we discuss our efforts in the atroposelective synthesis of different types of axially chiral compounds, including biaryls, atropisomeric styrenes, and C-N atropisomers, via transition metal-catalyzed enantioselective C-H activation strategies. To this end, we have developed several approaches, including the chiral transient directing group (<i>c</i>TDG) strategy using catalytic Pd(OAc)<sub>2</sub> and <i>tert</i>-leucine (Tle), as well as catalytic enantioselective systems involving Pd(II)/chiral phosphoric acid (CPA), Pd(II)/l-pyroglutamic acid (<i>p</i>Glu), Pd(0)/norbornene cooperative catalysis with a chiral biimidazoline (BiIM) ligand, and Co(II)/salicyloxazoline (Salox).At the outset, we successfully applied the <i>c</i>TDG strategy to access axially chiral biaryl aldehydes through Pd-catalyzed atroposelective C-H olefination, alkynylation, allylation, naphthylation, and alkylation. The efficacy of these methods has been demonstrated in the enantioselective synthesis of chiral aldehyde catalysts and natural products, such as TAN-1085, (+)-isochizandrin, and (+)-steganone. To facilitate the synthesis of biaryl atropisomers with diverse functionalities, we developed a novel Pd(II)/CPA catalytic system, which enables the preparation of various axially chiral quinolines, biaryl-2-amines, and atropisomeric biaryls bearing chalcogenoether units with high enantioselectivities. The Pd(II)/CPA system also allows for the synthesis of more challenging conjugated diene-based axially chiral styrenes.Nonbiaryl atropisomers, such as axially chiral styrenes and anilides, present synthetic challenges due to their conformational instability and higher degree of rotational freedom compared to their biaryl counterparts. We have addressed these challenges and achieved the highly efficient synthesis of atropisomeric styrenes and anilides using Pd(II)/<i>p</i>Glu and Pd(0)/norbornene/BiIM catalysis. In addition to palladium catalysis, cobalt(II)/Salox catalysis has also been developed for the construction of chiral biaryls, atropisomers with vicinal C-N and C-C stereogenic axes, remote distinct C-N diaxes, and chiral calix[4]arenes featuring both inherent and axial chirality. We anticipate that the enantioselective C-H activation strategy will find broad applications in the construction of synthetically useful axially chira","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"58 9","pages":"1562-1579"},"PeriodicalIF":16.4,"publicationDate":"2025-05-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143950847","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":"Three-Dimensional Polymer Micelles Formed by Crystallization-Driven Self-Assembly","authors":"Jingjie Jiang, Mitchell A. Winnik","doi":"10.1021/acs.accounts.5c00145","DOIUrl":"https://doi.org/10.1021/acs.accounts.5c00145","url":null,"abstract":"Polymer self-assembly plays a crucial role across various fields, such as biomedicine, catalysis, and optoelectronics. Over the years, self-assembly in solution has attracted significant interest. In 2007, our group, in collaboration with Prof. Ian Manners, published a groundbreaking article in <i>Science</i> on living crystallization-driven self-assembly (CDSA) of amphiphilic block copolymers featuring a crystalline core-forming block. This study focused on polyferrocenylsilane block copolymers (PFS BCPs). Living CDSA operates similarly to living polymerization, enabling the precise fabrication of micelles with predictable shapes and dimensions. The crystalline nature of the core-forming block promotes the formation of structures with low interfacial curvature, such as cylinders and platelets, which are rarely formed in traditional self-assembly techniques based on microphase separation.","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"99 1","pages":""},"PeriodicalIF":18.3,"publicationDate":"2025-05-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143910192","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":"Advancing Total Synthesis Through Skeletal Editing.","authors":"Reem Al-Ahmad, Mingji Dai","doi":"10.1021/acs.accounts.5c00030","DOIUrl":"https://doi.org/10.1021/acs.accounts.5c00030","url":null,"abstract":"&lt;p&gt;&lt;p&gt;ConspectusTotal synthesis has long been a proving ground for advancing chemical thought, pushing chemists to develop strategies that not only replicate nature's complexity but often surpass it. The pursuit of efficiency, practicality, and elegance continues to challenge and reshape the guiding principles of total synthesis. In recent years, skeletal editing has emerged as a powerful strategy for reconfiguring skeletal frameworks in ways that were previously difficult to imagine. Unlike conventional chemical synthesis approaches, which primarily rely on the logic of bond construction reactions and functional group manipulations, skeletal editing introduces elements that allow for atom insertion, deletion, and exchange and skeletal rearrangement/reorganization by harnessing the potential energy and reactivity of certain structural motifs and morphing them into new electronic and spatial configurations. The logic of modern skeletal editing has been fueling the development of new editing methods and advancing the fields of total synthesis, medicinal chemistry, materials science, and others.In this Account, we detail our program using skeletal editing-based retrosynthetic logic to facilitate natural product synthesis. We first highlight two one-carbon insertion editing strategies utilizing the Ciamician-Dennstedt rearrangement and the Büchner-Curtius-Schlotterbeck ring expansion to streamline the total syntheses of complanadine and phleghenrine &lt;i&gt;Lycopodium&lt;/i&gt; alkaloids. We next present our synthesis of crinipellin and gibberellin diterpenes by leveraging the facile synthesis and intrinsic strain of cyclobutanes as precursors to challenging cyclopentanes via cut-and-insert editing (crinipellins) or C-C bond migratory ring expansion (GA&lt;sub&gt;18&lt;/sub&gt;). Toward the end, we describe our early efforts in orchestrating structural rearrangement and functional group pairing reactions to access seven monoterpene indole alkaloids and highlight the divergent potential of skeletal editing. Each of the five examples follows a build-edit-decorate workflow, inspired by Schreiber's build-couple-pair in diversity-oriented synthesis. In the build stage, key scaffolds are efficiently assembled from starting materials with matched reactivity. The edit stage morphs these scaffolds to the desired but more challenging ones encoded by the target molecules, reminiscent of Corey's application of rearrangement transforms as a topological strategy. The decorate stage introduces additional functional groups and adjusts oxidation states to complete the total synthesis, similar to the oxidase phase of Baran's two-phase synthesis. The essence of skeletal editing-based retrosynthetic analysis is to identify latent structural relationships between the readily assembled key scaffolds constructed in the build stage and the desired ones encoded by the target molecules as well as proper editing methods to transform the former into the latter with precision. The build-edit-decorate ","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"58 9","pages":"1392-1406"},"PeriodicalIF":16.4,"publicationDate":"2025-05-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12060283/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143950653","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":"Carbenoid Reactions Promoted by Solids: From Lewis to Brønsted Catalysts.","authors":"Antonio Leyva-Pérez, Marta Mon, Yongkun Zheng","doi":"10.1021/acs.accounts.5c00159","DOIUrl":"https://doi.org/10.1021/acs.accounts.5c00159","url":null,"abstract":"<p><p>ConspectusDiazocarbonyl compounds have become essential tools in organic synthesis, due to their ability to in situ generate reactive carbenes and be inserted in a variety of otherwise stable bonds, such as C-H, C-C, H-O, and so on. However, a soluble metal salt or complex catalyst is generally required to selectively activate and couple the carbene, and the metals employed so far are expensive (Rh, Au, Ag, Cu) and often unrecoverable. It is noteworthy that the price of ligands can make a cheaper metal catalyst (i.e., Cu) as expensive as other ligand-free noble metal catalysts. In the realm of modern sustainable chemistry, most of these methodologies are now unacceptable and must be adapted, and simple strategies for that include carbene photoactivation and the use of recoverable solid catalysts. Unfortunately, despite research in the field of carbene insertion reactions that has extended now for more than 50 years, examples with solid catalysts are still minor, and efficient solid catalysts have only been reported in the last two decades.This Account shows the journey faced by our group in the last eight years to find solid catalysts for challenging carbene insertion reactions, employing diazocarbonyl compounds as carbene precursors. We will contextualize our results with those of previous solid catalysts. The discovery in 2017 that a quasi-linear Pd₄ cluster stabilized within a metal-organic framework (MOF) was able to catalyze the Büchner and other carbene insertion reactions, spurred the design of supported metal clusters as catalysts for a variety of carbene insertion reactions. The Pd₄-MOF could be reused 20 times in batch and implemented in a flow process. Following this, other catalytic solids, including Au and Ag as metals, not only in the same MOF but also on solid oxides and zeolites as supports, showed good activity for carbene insertion reactions and were also recoverable and reusable.Our journey temporarily finishes in 2024 when \"blank\" experiments with a dealuminated zeolite surprisingly revealed that this simple solid acid, without any metal, easily activates the diazocarbonyl compound and catalyzes a variety of carbene insertion reactions, thus providing a cheap, commercially available, and reusable solid catalyst for these challenging reactions. Overall, rapid progress in solid-catalyzed diazocarbonyl compound activation, carbene formation, and insertion reactions has been achieved during these years, moving from expensive and difficult to prepare solid catalysts based on supported metal clusters to simple acid zeolites, pointing to confined Brønsted acids as the catalysts to study in the near future.</p>","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"58 9","pages":"1534-1546"},"PeriodicalIF":16.4,"publicationDate":"2025-05-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12060285/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143950670","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":"Let There Be Heat: Silica-Coated Gold Nanoparticles as Photothermal Reactors for Chemical Synthesis.","authors":"Aritra Biswas, Nir Lemcoff, Yossi Weizmann","doi":"10.1021/acs.accounts.5c00072","DOIUrl":"https://doi.org/10.1021/acs.accounts.5c00072","url":null,"abstract":"&lt;p&gt;&lt;p&gt;ConspectusThe heating of matter upon interacting with light is a fundamental process ubiquitous in the natural world. With the rise of nanotechnology over the past decades, a variety of nanomaterials capable of converting light into heat have been discovered and their physicochemical properties investigated. Perhaps the most exotic is the photothermal heating of metallic nanocrystals via surface plasmons. Here an incoming electromagnetic wave triggers the oscillation of the nanoparticle's electron cloud. When in resonance, this generates an enormous increase to the absorption coefficient, enabling more energy to dissipate as heat. The plasmonic phenomenon has an incredibly diverse range of functions, from the vibrant coloration of medieval stained-glass windows to the localization and enhancement of light at the nanoscale level. Plasmonic heating or thermoplasmonics is a relatively new addition that has gained popularity mainly through applications in therapeutics and biotechnology. With this Account, we aim to put a spotlight on the use of thermoplasmonics to drive chemical synthesis, a rapidly expanding area of research with immense potential.Throughout the long tradition of chemical synthesis, chemists have rarely deviated from the typical oven or hot plate to set and maintain a homogeneous temperature within the reaction vessel. In contrast, the use of thermoplasmonic nanomaterials can introduce heterogeneity to the heating profile of a reaction by forming steep temperature gradients near the surface of nanoparticles. Additionally, photothermal conversion enables heat activated processes to benefit from the advantages of light initiation, e.g., contactless activation and spatial control. Thus, thermoplasmonics offers an attractive alternative to the long-standing norm.Several early studies demonstrated the power of this method, taking advantage of the localized heating to carry out reactions with minimal change to the bulk temperature of the surrounding medium. However, tapping into this potential can be very challenging as colloidal solutions tend to aggregate even with small changes to the environment. Different strategies have been utilized to overcome this obstacle, for example embedding particles into glass or other heterogeneous substrates. Our group has experimented with coating gold nanostructures with a silica shell. This ensures the structural and colloidal stability that is critical for thermoplasmonic chemistry. Recently, we applied this methodology to advance olefin metathesis, the synthesis of iron oxide (IO), palladium (Pd) and silver (Ag) nanoparticles, and the formation of various metal-organic frameworks (MOFs). In addition, highly stable hybrid materials could be isolated as composites of plasmonic particles with polymers, MOFs, and other nanostructures. The large variety of reaction conditions and the different precursors, additives, and catalysts that our method proved to be compatible with highlight the versatility","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"58 9","pages":"1424-1434"},"PeriodicalIF":16.4,"publicationDate":"2025-05-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12060276/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143950992","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":"Three-Dimensional Polymer Micelles Formed by Crystallization-Driven Self-Assembly","authors":"Jingjie Jiang,&nbsp; and ,&nbsp;Mitchell A. Winnik*,&nbsp;","doi":"10.1021/acs.accounts.5c0014510.1021/acs.accounts.5c00145","DOIUrl":"https://doi.org/10.1021/acs.accounts.5c00145https://doi.org/10.1021/acs.accounts.5c00145","url":null,"abstract":"<p >Polymer self-assembly plays a crucial role across various fields, such as biomedicine, catalysis, and optoelectronics. Over the years, self-assembly in solution has attracted significant interest. In 2007, our group, in collaboration with Prof. Ian Manners, published a groundbreaking article in <i>Science</i> on living crystallization-driven self-assembly (CDSA) of amphiphilic block copolymers featuring a crystalline core-forming block. This study focused on polyferrocenylsilane block copolymers (PFS BCPs). Living CDSA operates similarly to living polymerization, enabling the precise fabrication of micelles with predictable shapes and dimensions. The crystalline nature of the core-forming block promotes the formation of structures with low interfacial curvature, such as cylinders and platelets, which are rarely formed in traditional self-assembly techniques based on microphase separation.</p><p >Over the past two decades, we have pioneered a range of strategies to create one-dimensional (1D), 2D, 3D, and hierarchical uniform PFS BCP structures via CDSA. This method has also been extended to other semicrystalline polymer systems to produce regular and uniform assemblies. While 1D and 2D micelles have been extensively studied, the fabrication of 3D structures remains relatively rare. Nature, however, possesses exquisite 3D structures. Although CDSA has generated some 3D structures, it has not yet achieved the complexity found in nature. Researchers continue to push boundaries toward creating more intricate 3D structures.</p><p >In this Account, we summarize our research advancements on 3D structure fabrication via CDSA. The free energy of the system, influenced by various factors, ultimately determines micellar morphology and growth behavior. Our work has led to the formation of branched structures through multistep seeded growth processes, incorporating PFS homopolymers (HP) with PFS BCP, manipulating the cooling rate, adjusting the corona block composition, controlling polymer dispersity, and varying solvents. Further innovations involved the use of organic sacrificial templates to produce hollow fiber-basket polymersomes and the application of inorganic substrates for surface micelle growth, yielding organic–inorganic hybrid materials with tailored functionalities. A significant breakthrough was the development of protocols for generating uniform polymeric spherulites and their precursors in solution. Although spherulites are common in bulk polymer materials and materials found in fields such as geology and biology, they have not been observed from block polymers in solution. We uncovered a novel CDSA mechanism in which defects in lamellar precursors act as a critical driver for constructing 3D architectures. To achieve intricate, bioinspired, and uniform 3D structures, further efforts will focus on enhancing structural control and integrating multifunctional properties.</p>","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"58 10","pages":"1683–1695 1683–1695"},"PeriodicalIF":16.4,"publicationDate":"2025-05-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144088579","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":"Enchanting Realm of Five-Membered Rare-Earth Metallacycles","authors":"Wei Liu, Dajiang Huang, Junnian Wei, Wen-Xiong Zhang","doi":"10.1021/acs.accounts.5c00168","DOIUrl":"https://doi.org/10.1021/acs.accounts.5c00168","url":null,"abstract":"Metallacycles, derivatives of carbocyclic compounds wherein a metal atom replaces at least one carbon center, have been a constant powerhouse in organic synthesis. While metallacycles of main-group, transition, and actinide metals have been extensively studied, those incorporating rare-earth (RE) elements (Sc, Y, and lanthanides) have remained elusive primarily due to synthetic challenges. Nevertheless, the electropositive character of these elements and the resulting polarization of RE–C bonds, along with the intrinsic synergistic effects within metallacycles, endow RE metallacycles with unique properties and a rich, yet largely untapped, reaction chemistry. In this Account, we present the development and applications of five-membered RE metallacycles.","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"35 1","pages":""},"PeriodicalIF":18.3,"publicationDate":"2025-05-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143910193","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":"Enchanting Realm of Five-Membered Rare-Earth Metallacycles","authors":"Wei Liu,&nbsp;Dajiang Huang,&nbsp;Junnian Wei and Wen-Xiong Zhang*,&nbsp;","doi":"10.1021/acs.accounts.5c0016810.1021/acs.accounts.5c00168","DOIUrl":"https://doi.org/10.1021/acs.accounts.5c00168https://doi.org/10.1021/acs.accounts.5c00168","url":null,"abstract":"&lt;p &gt;Metallacycles, derivatives of carbocyclic compounds wherein a metal atom replaces at least one carbon center, have been a constant powerhouse in organic synthesis. While metallacycles of main-group, transition, and actinide metals have been extensively studied, those incorporating rare-earth (RE) elements (Sc, Y, and lanthanides) have remained elusive primarily due to synthetic challenges. Nevertheless, the electropositive character of these elements and the resulting polarization of RE–C bonds, along with the intrinsic synergistic effects within metallacycles, endow RE metallacycles with unique properties and a rich, yet largely untapped, reaction chemistry. In this Account, we present the development and applications of five-membered RE metallacycles.&lt;/p&gt;&lt;p &gt;Over the past decade, we have successfully synthesized a variety of five-membered all-carbon rare-earth metallacycles using two key synthetic strategies: (i) transmetalation, which has been employed to prepare RE metallacyclopentadienes and &lt;i&gt;spiro&lt;/i&gt;-metallacyclopentadienes, which, featuring various ligand systems, provide distinct coordination environments around the RE center, significantly influencing their reactivity, and (ii) transmetalation and reduction, enabling the synthesis of RE &lt;i&gt;spiro&lt;/i&gt;-metallacyclopentenes and 2-butene tetraanion (BTA)-bridged dinuclear RE metallacyclopentenes. The reduction process proceeds via either self-disproportionation of metallacyclopentadienes or reduction by divalent RE centers or alkali metals. These metallacycles represent the first instances of such RE-containing metallacyclic ring structures.&lt;/p&gt;&lt;p &gt;Our investigations into these metallacycles have uncovered unique reactivities and new reaction modes. The high intrinsic reactivity and multiple reactive sites of rare-earth metallacycles enable them not only to activate small molecules efficiently but also to exhibit distinct activation modes for some small molecules. For instance, reactions of RE metallacyclopentadienes with carbodiimides showcase diverse insertion/rearrangement chemistry, influenced by various factors such as number of equivalents of carbodiimide and the solvent choice. The RE metallacyclopentadiene-mediated [3 + 1] fragmentation of white phosphorus demonstrates an activation mode markedly different from that observed with main-group and transition metal analogs. Moreover, the discovery of cross-carbanion coupling at RE centers and RE-metal-mediated ring-opening metathesis of benzene introduces new reaction modes, demonstrating that, with rational design, RE metals can exhibit properties similar to or even surpassing those of transition metals. These reaction modes have further led to the development of applications for RE metallacycles in synthetic chemistry.&lt;/p&gt;&lt;p &gt;Additionally, some novel properties of these rare-earth metallacycles have been uncovered, stemming from their unique geometric and electronic structures. Structural analysis and theoretical calculations hav","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"58 10","pages":"1696–1709 1696–1709"},"PeriodicalIF":16.4,"publicationDate":"2025-05-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144088410","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":"Multicomponent Metallacages via the Integrative Self-Assembly of Pt(II) Nodes with Multiple Pyridyl and Carboxylate Ligands","authors":"Yali Hou, Zeyuan Zhang, Mingming Zhang","doi":"10.1021/acs.accounts.5c00085","DOIUrl":"https://doi.org/10.1021/acs.accounts.5c00085","url":null,"abstract":"In recent years, multicomponent self-assembly has emerged as a pivotal strategy in supramolecular chemistry, enabling the construction of artificial systems with enhanced functionalities that surpass those of individual molecular components. These assemblies have garnered significant interest due to their potential applications in molecular recognition, catalysis, and biomedical engineering. However, achieving precise control over the assembly process remains a significant challenge, as increased structural complexity often results in thermodynamic mixtures, limiting their practical applications. In this context, metal-coordination-driven multicomponent self-assembly has emerged as a promising strategy, as the moderate strength and good directionality of metal–ligand bonds ensure the formation of discrete supramolecular architectures with well-defined structures and geometries. Notably, the integration of pyridyl and carboxylate donors with <i>cis</i>-Pt(II) nodes offers an effective approach for constructing multicomponent metallacages. This method is particularly attractive due to its ability to enable precise heteroleptic assembly, along with the accessibility and tunability of the ligands, which impart desirable photophysical properties and potential anticancer activities.","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"14 1","pages":""},"PeriodicalIF":18.3,"publicationDate":"2025-05-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143901800","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":"Multicomponent Metallacages via the Integrative Self-Assembly of Pt(II) Nodes with Multiple Pyridyl and Carboxylate Ligands","authors":"Yali Hou,&nbsp;Zeyuan Zhang and Mingming Zhang*,&nbsp;","doi":"10.1021/acs.accounts.5c0008510.1021/acs.accounts.5c00085","DOIUrl":"https://doi.org/10.1021/acs.accounts.5c00085https://doi.org/10.1021/acs.accounts.5c00085","url":null,"abstract":"&lt;p &gt;In recent years, multicomponent self-assembly has emerged as a pivotal strategy in supramolecular chemistry, enabling the construction of artificial systems with enhanced functionalities that surpass those of individual molecular components. These assemblies have garnered significant interest due to their potential applications in molecular recognition, catalysis, and biomedical engineering. However, achieving precise control over the assembly process remains a significant challenge, as increased structural complexity often results in thermodynamic mixtures, limiting their practical applications. In this context, metal-coordination-driven multicomponent self-assembly has emerged as a promising strategy, as the moderate strength and good directionality of metal–ligand bonds ensure the formation of discrete supramolecular architectures with well-defined structures and geometries. Notably, the integration of pyridyl and carboxylate donors with &lt;i&gt;cis&lt;/i&gt;-Pt(II) nodes offers an effective approach for constructing multicomponent metallacages. This method is particularly attractive due to its ability to enable precise heteroleptic assembly, along with the accessibility and tunability of the ligands, which impart desirable photophysical properties and potential anticancer activities.&lt;/p&gt;&lt;p &gt;This Account provides a comprehensive overview of our work on the design, preparation, and functionalization of multicomponent metallacages via the heteroleptic assembly of pyridyl and carboxylate ligands with &lt;i&gt;cis&lt;/i&gt;-Pt(II) nodes. By strategically tailoring the ligand structures and adjusting the number of coordination sites, we have successfully constructed multicomponent metallacages with diverse geometries, including tetragonal and hexagonal prisms, triple-cavity ladders, truncated octahedra, and cyclic bis[2]catenanes, etc. In particular, we highlight the use of functional pyridyl ligands, such as tetraphenylethylene, hexaphenylbenzene, perylene diimide, and porphyrin derivatives, to explore the applications of these metallacages. Tetraphenylethylene and hexaphenylbenzene derivatives are propeller-shaped molecules with aggregation-induced emission properties, enhancing the emission of the metallacages both in solution and the solid state. Perylene diimide derivatives, with their electron-deficient, planar conjugated structures, contribute to strong emission in solution, thereby improving the host–guest chemistry and luminescent properties of the metallacages. Porphyrin derivatives, owing to their planar structures and excellent photosensitivity, endow the metallacages with significant photocatalytic capabilities. Additionally, other ligands, such as phenanthroline and triazine derivatives, have been employed to impart antibacterial and SO&lt;sub&gt;2&lt;/sub&gt; adsorption properties, respectively, to the metallacages. Furthermore, metallacage-cross-linked supramolecular networks exhibit enhanced mechanical properties and superior processability, making them promisin","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"58 10","pages":"1644–1656 1644–1656"},"PeriodicalIF":16.4,"publicationDate":"2025-05-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144088368","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}