Accounts of materials research最新文献

{"title":"Facile Strategies for Incorporating Chiroptical Activity into Organic Optoelectronic Devices","authors":"Hanna Lee, Danbi Kim, Jeong Ho Cho and Jung Ah Lim*, ","doi":"10.1021/accountsmr.4c0037410.1021/accountsmr.4c00374","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00374https://doi.org/10.1021/accountsmr.4c00374","url":null,"abstract":"<p >Chiral optoelectronics, which utilize the unique interactions between circularly polarized (CP) light and chiral materials, open up exciting possibilities in advanced technologies. These devices can detect, emit, or manipulate light with specific polarization, enabling applications in secure communication, sensing, and data processing. A key aspect of chiral optoelectronics is the ability to generate or detect optical and electrical signals by controlling or distinguishing CP light based on its polarization direction. This capability is rooted in the selective interaction of CP light with the stereogenic (non-superimposable) molecular geometry of chiral substances, wherein the polarization of CP light aligns with the intrinsic asymmetry of the material. Among the diverse chiral materials explored for this purpose, π-conjugated molecules offer special advantages due to their tunable optoelectronic properties, efficient light–matter interactions, and cost-effective processability. Recent advancements in π-conjugated molecule research have demonstrated their ability to generate strong chiroptical responses, thereby paving the way for compact and multifunctional device designs. Building on these unique advantages, π-conjugated molecules have advanced organic electronics into rapidly evolving technological fields. The combination of chiral π-conjugated molecules with organic electronics is anticipated to simplify the fabrication of chiroptical devices, thereby lowering technical barriers and accelerating progress in chiral optoelectronics.</p><p >This Account introduces strategies for incorporating chiroptical activity into organic optoelectronic devices, focusing on two main approaches: direct incorporation of chiroptical activity into π-conjugated polymer semiconductors and integration of chiral organic nanoarchitectures with conventional organic optoelectronic devices. In the first approach, we especially highlight simple methods to induce chiroptical activity in various achiral π-conjugated polymers through the transfer of chirality from small chiral molecules. This hybrid approach effectively combines the excellent electrical properties and various optical transition properties of achiral polymers with the strong chiroptical activity of small molecules. Moreover, we address a fundamental challenge in achieving chiroptical transitions in planar π-conjugated polymers, demonstrating the development of low-bandgap π-conjugated polymers that exhibit both strong chiroptical activity and excellent electrical performance. Another approach, incorporating chiroptical activity into existing organic optoelectronic devices, which have already achieved significant performance advances, presents an effective strategy for high-performance chiral optoelectronics. For this purpose, we introduce the use of supramolecular assemblies of π-conjugated molecules to impart chiroptical responses into high-performance optoelectronic systems, utilizing efficient charge ","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"6 4","pages":"434–446 434–446"},"PeriodicalIF":14.0,"publicationDate":"2025-03-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143867535","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Facile Strategies for Incorporating Chiroptical Activity into Organic Optoelectronic Devices","authors":"Hanna Lee, Danbi Kim, Jeong Ho Cho, Jung Ah Lim","doi":"10.1021/accountsmr.4c00374","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00374","url":null,"abstract":"Chiral optoelectronics, which utilize the unique interactions between circularly polarized (CP) light and chiral materials, open up exciting possibilities in advanced technologies. These devices can detect, emit, or manipulate light with specific polarization, enabling applications in secure communication, sensing, and data processing. A key aspect of chiral optoelectronics is the ability to generate or detect optical and electrical signals by controlling or distinguishing CP light based on its polarization direction. This capability is rooted in the selective interaction of CP light with the stereogenic (non-superimposable) molecular geometry of chiral substances, wherein the polarization of CP light aligns with the intrinsic asymmetry of the material. Among the diverse chiral materials explored for this purpose, π-conjugated molecules offer special advantages due to their tunable optoelectronic properties, efficient light–matter interactions, and cost-effective processability. Recent advancements in π-conjugated molecule research have demonstrated their ability to generate strong chiroptical responses, thereby paving the way for compact and multifunctional device designs. Building on these unique advantages, π-conjugated molecules have advanced organic electronics into rapidly evolving technological fields. The combination of chiral π-conjugated molecules with organic electronics is anticipated to simplify the fabrication of chiroptical devices, thereby lowering technical barriers and accelerating progress in chiral optoelectronics.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"2 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-03-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143532688","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Engineering Hierarchy to Porous Organic Cages for Biomimetic Catalytic Applications","authors":"Jing-Wang Cui, Si-Hua Liu, Liang-Xiao Tan and Jian-Ke Sun*, ","doi":"10.1021/accountsmr.4c0040210.1021/accountsmr.4c00402","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00402https://doi.org/10.1021/accountsmr.4c00402","url":null,"abstract":"<p >In nature, hierarchy is a core organizational principle intricately woven into biological systems, facilitating the compartmentalization of enzymes within living cells. This spatial arrangement enables multistep metabolic reactions to occur simultaneously with remarkable efficiency and precision. Inspired by this, significant progress has been made in artificial biomimetic heterogeneous catalytic systems using porous materials like metal–organic frameworks, porous organic polymers, and zeolites. Among these, molecular cages, with their well-defined cavities, stand out as synthetic models for enzyme-mimic catalysis. They not only provide biomimetic microenvironments for substrate binding, mimicking the highly specific and efficient interactions observed in natural enzymatic systems, but also integrate active centers within confined nanoscale spaces, enabling synergistic functionality. However, research in cage-based biomimetic catalysts has largely focused on tailoring the cavity environment─such as optimizing cavity size, pore geometry, and functional groups on the pore walls─to regulate catalytic processes, while comparatively less attention has been given to the catalytic role of metal centers, akin to the critical function in natural metalloenzymes. While metal nodes in metal–organic cages can act as active sites, their catalytic efficiency may be hindered by coordination saturation. Moreover, the restricted (sub)nanoscale space of molecular cage reactors limits their capacity to host larger active sites or accommodate bulky substrates. Thus, rationally engineering the confined spaces and optimizing the spatial arrangement of active sites within molecular cage-based catalytic systems is essential for advancing the field and unlocking their full potential.</p><p >This Account leverages recent advancements in molecular cage materials, particularly porous organic cages (POCs), to design hierarchical POCs as versatile platforms for biomimetic catalytic systems. It begins by defining hierarchical POCs, outlining their structural and compositional hierarchies, and highlighting the significant potential they hold for biomimetic catalysis. We then explore the approaches for introducing hierarchy into POCs, discussing how insights from both serendipitous experimental data (shear flow assisted crystallization) and deliberate design lead to the development of specific strategies. These include noncovalent and covalent/coordination-driven assembly approaches for creating architectural hierarchies with micro-, meso-, and/or macropores. By integrating diverse active sites, such as metal clusters (MCs), metal complexes, and enzymes, within these (hierarchical) pores, we establish component hierarchies. The focus then shifts to biomimetic catalysis, where we emphasize the precise optimization of active site size, location, and the surrounding microenvironment to enhance catalytic performance. Additionally, we highlight the importance of communication and ","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"6 4","pages":"484–498 484–498"},"PeriodicalIF":14.0,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143867527","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Engineering Hierarchy to Porous Organic Cages for Biomimetic Catalytic Applications","authors":"Jing-Wang Cui, Si-Hua Liu, Liang-Xiao Tan, Jian-Ke Sun","doi":"10.1021/accountsmr.4c00402","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00402","url":null,"abstract":"In nature, hierarchy is a core organizational principle intricately woven into biological systems, facilitating the compartmentalization of enzymes within living cells. This spatial arrangement enables multistep metabolic reactions to occur simultaneously with remarkable efficiency and precision. Inspired by this, significant progress has been made in artificial biomimetic heterogeneous catalytic systems using porous materials like metal–organic frameworks, porous organic polymers, and zeolites. Among these, molecular cages, with their well-defined cavities, stand out as synthetic models for enzyme-mimic catalysis. They not only provide biomimetic microenvironments for substrate binding, mimicking the highly specific and efficient interactions observed in natural enzymatic systems, but also integrate active centers within confined nanoscale spaces, enabling synergistic functionality. However, research in cage-based biomimetic catalysts has largely focused on tailoring the cavity environment─such as optimizing cavity size, pore geometry, and functional groups on the pore walls─to regulate catalytic processes, while comparatively less attention has been given to the catalytic role of metal centers, akin to the critical function in natural metalloenzymes. While metal nodes in metal–organic cages can act as active sites, their catalytic efficiency may be hindered by coordination saturation. Moreover, the restricted (sub)nanoscale space of molecular cage reactors limits their capacity to host larger active sites or accommodate bulky substrates. Thus, rationally engineering the confined spaces and optimizing the spatial arrangement of active sites within molecular cage-based catalytic systems is essential for advancing the field and unlocking their full potential.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"1 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143495901","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Three-Dimensional Photo-Cross-Linkers for Nondestructive Photopatterning of Electronic Materials","authors":"Shahid Ameen, Myeongjae Lee, Moon Sung Kang, Jeong Ho Cho and BongSoo Kim*, ","doi":"10.1021/accountsmr.4c0036510.1021/accountsmr.4c00365","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00365https://doi.org/10.1021/accountsmr.4c00365","url":null,"abstract":"<p >Solution-processed electronics have shown promise in cost-effective manufacturing, but face challenges in precisely and accurately placing electronic materials. Traditional methods, such as photolithography with photoresists, involve complex steps that can damage electronic materials. Alternatives such as orthogonal patterning and inkjet printing are limited by the difficulty of finding compatible chemicals that do not dissolve underlying layers, while nanoimprinting lacks compatibility with high-throughput processes and suffers from poor chemical robustness. Conventional photo-cross-linking approaches have used organic or polymeric agents to pattern electronic layers, but the consecutive application of photo-cross-linking processes for patterning and stacking of multiple electronic materials typically led to degradation of the intrinsic properties of the materials.</p><p >To overcome these issues, we have demonstrated a promising photopatterning strategy of using highly efficient, three-dimensional photo-cross-linkers bearing multiple phenyl azides. Specifically, electronic materials hosting a minimal amount of the photo-cross-linkers were photo-cross-linked under UV through a photomask, followed by subsequent removal of the uncross-linked parts using a developing solvent. This method produces a patterned electronic layer that maintains chemical and physical stability while enhancing the thermal and mechanical stabilities. The successive patterning of electronic materials in this approach has precise control over parallel or vertical stacking of high-resolution electronic material layers without optical/electrical property loss. This Account provides an overview of our efforts toward photopatterning electronic materials in the field of polymer thin film transistors (PTFTs), organic light-emitting diodes (OLEDs), and quantum-dot light-emitting diodes (QD-LEDs). First, two azide-based multibridged photo-cross-linkers (i.e., 4Bx and 6Bx) were developed and applied to fabricate all-solution-processed PTFTs. These cross-linkers have excellent cross-linkability compared to a conventional bifunctional photo-cross-linker (i.e., 2Bx), leading to fabricating thin-film electronic layer patterns and acquiring chemical resistance of each layer. Moreover, they effectively reduce leakage current and enhance the electrical strength in dielectric layers. This research underscores the crucial role of efficient cross-linkers in achieving all-solution-processed, all-photopatterned organic electronic devices while preserving their intrinsic electrical properties of employed semiconducting polymers. These cross-linkers have also been applied for OLEDs, which produces high-resolution photopatterned light-emitting polymer semiconductors. Furthermore, azide-based photo-cross-linking chemistry has been applied to the patterning of luminescent QDs. A breakthrough approach of utilizing a bulky isopropyl group-containing photo-cross-linker (i.e., IP-6-LiXer) has been de","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"6 3","pages":"340–351 340–351"},"PeriodicalIF":14.0,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143714024","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Toward Sustainable Materials: From Lignocellulosic Biomass to High-Performance Polymers","authors":"Jignesh S. Mahajan, Eric R. Gottlieb, Jung Min Kim, Thomas H. Epps, III","doi":"10.1021/accountsmr.4c00359","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00359","url":null,"abstract":"Lignocellulosic biomass is an ideal feedstock for the next generation of sustainable, high-performance, polymeric materials. Although lignin is a highly available and low-cost source of natural aromatics, it is commonly burned for heat or disposed of as waste. The use of lignin for new materials introduces both challenges and opportunities with respect to incumbent petrochemical-based compounds. These considerations are derived from two fundamental aspects of lignin: its recalcitrant/heterogeneous nature and aromatic methoxy substituents. This Account highlights four key efforts from the Epps group and collaborators that established innovative methods/processes to synthesize polymers from lignin deconstruction products to unlock application potential, with a particular focus on the polymerization of biobased monomer mixtures, development of structure–property–processing relationships for diverse feedstocks, functional benefits of methoxy substituents, and scalability of lignin deconstruction.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"80 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143463265","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Toward Sustainable Materials: From Lignocellulosic Biomass to High-Performance Polymers","authors":"Jignesh S. Mahajan, Eric R. Gottlieb, Jung Min Kim and Thomas H. Epps III*, ","doi":"10.1021/accountsmr.4c0035910.1021/accountsmr.4c00359","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00359https://doi.org/10.1021/accountsmr.4c00359","url":null,"abstract":"<p >Lignocellulosic biomass is an ideal feedstock for the next generation of sustainable, high-performance, polymeric materials. Although lignin is a highly available and low-cost source of natural aromatics, it is commonly burned for heat or disposed of as waste. The use of lignin for new materials introduces both challenges and opportunities with respect to incumbent petrochemical-based compounds. These considerations are derived from two fundamental aspects of lignin: its recalcitrant/heterogeneous nature and aromatic methoxy substituents. This Account highlights four key efforts from the Epps group and collaborators that established innovative methods/processes to synthesize polymers from lignin deconstruction products to unlock application potential, with a particular focus on the polymerization of biobased monomer mixtures, development of structure–property–processing relationships for diverse feedstocks, functional benefits of methoxy substituents, and scalability of lignin deconstruction.</p><p >First, lignin-derivable polymethacrylate systems were probed to investigate the polymerization behavior of methacrylate monomers and predict thermomechanical properties of polymers from monomer mixtures. Notably, the glass transition temperatures (<i>T</i><sub>g</sub>s) of lignin-derivable polymethacrylates (∼100–200 °C) were comparable to, or significantly above, those of petroleum-based analogues, such as polystyrene (∼100 °C), and the <i>T</i><sub>g</sub>s of the complex, biobased copolymers could be predicted by the Fox equation prior to biomass deconstruction.</p><p >Second, an understanding of structure–property relationships in polymethacrylates was applied to create performance-advantaged pressure-sensitive adhesives (PSAs) using phenolic-rich bio-oil obtained from the reductive catalytic fractionation of poplar wood. The use of actual lignin-derived monomers as the starting material was an important step because it underscored that nanostructure-forming, multiblock polymers could be readily made despite the complexity of real lignin deconstruction products. This work also highlighted that lignin-based phenolics could be used to make colorless/odorless PSAs, without complex separations/purifications, and still perform as well as commercial adhesives.</p><p >Third, an intensified reductive catalytic deconstruction (RCD) process was developed to deconstruct lignin at ambient conditions, and the deconstructed products were successfully employed in 3D printing. The reactive distillation-RCD process operated at ambient pressure using a low-volatility and biobased solvent (glycerin) as a hydrogen donor, which reduced capital/operating costs, energy use, and safety hazards associated with conventional RCD. Technoeconomic analysis showed that such optimization could lead to a 60% reduction in cost to make the PSAs described above.</p><p >Fourth, lignin-derivable bisguaiacols/bissyringols were explored as potential alternatives to petroleum-derived","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"6 3","pages":"316–326 316–326"},"PeriodicalIF":14.0,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/accountsmr.4c00359","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713875","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Chiral Reticular Chemistry toward Functional Materials Discovery and Beyond","authors":"Wei Gong*, Yifei Gao, Jinqiao Dong, Yan Liu* and Yong Cui*, ","doi":"10.1021/accountsmr.4c0033710.1021/accountsmr.4c00337","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00337https://doi.org/10.1021/accountsmr.4c00337","url":null,"abstract":"<p >Reticular chemistry, pioneered by Omar Yaghi, is concerned with linking molecular building blocks into porous crystalline 2D or 3D architectures through coordination bonds (metal–organic frameworks, MOFs) or covalent bonds (covalent organic frameworks, COFs). The successful marriage of inorganic and organic chemistry in MOFs has provided vast combinations amenable to manufacturing enormous solid materials (>100,000 in Cambridge Crystallographic Data Centre) with atomic precision. Benefiting from the immanent component and structural diversity, as well as the accessible nanometer-scale spaces within which various matter can be manipulated and controlled, the reticular framework materials have in effect not only facilitated the development of basic chemistry but also revolutionized various fields of applications including gas storage and separation, heterogeneous catalysis, heat allocation, sensors, photovoltaics, fuel cells, and biomedicine, to just name a few. One particularly intriguing subset of reticular frameworks concerns those that have chiral elements or characteristics, which represent a unique class of extended porous solids that can implement enantiomerically selective applications and beyond. However, the development of this field is still at the embryonic stage as compared with that of achiral reticular frameworks. Herein, we summarize the progress in the development of “chiral reticular chemistry” through which a serial of homochiral or racemic reticular frameworks with novel topologies and functions can be targeted. To begin, we introduce the background of reticular chemistry and the potential of using chiral building blocks to assemble reticular frameworks, particularly MOFs. In the following section, we describe the synthetic diversity and complexity using enantiopure or racemic ligands and highlight the important role of enantiopurity engineering in affecting the ultimate products. To be more specific, we present (i) isotopological synthesis in which enantiopure or racemic ligands produce frameworks with the same net topology, where the racemic ligands form either racemic frameworks or conglomerates; (ii) intrinsically chiral net-dominated synthesis in which enantiopure or racemic ligands can form different underlying topologies or undergo distinct crystallization pathways; (iii) other atypical syntheses that typically come by way of serendipity, where the assembly mechanism is highly elusive (for example, the enantiomeric ligands of opposite chirality give rise to entirely different structures). Next, we discuss the applications of these unique reticular framework materials that are otherwise unachievable by conventional achiral materials or analogues, aiming to underline the unique role of chiral building blocks in reticular chemistry. Last, we point out future research directions of “chiral reticular chemistry”. Our Account aims to highlight the importance of chirality as a decisive parameter to control the ultimate str","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"6 5","pages":"550–562 550–562"},"PeriodicalIF":14.0,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144114693","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Chiral Reticular Chemistry toward Functional Materials Discovery and Beyond","authors":"Wei Gong, Yifei Gao, Jinqiao Dong, Yan Liu, Yong Cui","doi":"10.1021/accountsmr.4c00337","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00337","url":null,"abstract":"Reticular chemistry, pioneered by Omar Yaghi, is concerned with linking molecular building blocks into porous crystalline 2D or 3D architectures through coordination bonds (metal–organic frameworks, MOFs) or covalent bonds (covalent organic frameworks, COFs). The successful marriage of inorganic and organic chemistry in MOFs has provided vast combinations amenable to manufacturing enormous solid materials (>100,000 in Cambridge Crystallographic Data Centre) with atomic precision. Benefiting from the immanent component and structural diversity, as well as the accessible nanometer-scale spaces within which various matter can be manipulated and controlled, the reticular framework materials have in effect not only facilitated the development of basic chemistry but also revolutionized various fields of applications including gas storage and separation, heterogeneous catalysis, heat allocation, sensors, photovoltaics, fuel cells, and biomedicine, to just name a few. One particularly intriguing subset of reticular frameworks concerns those that have chiral elements or characteristics, which represent a unique class of extended porous solids that can implement enantiomerically selective applications and beyond. However, the development of this field is still at the embryonic stage as compared with that of achiral reticular frameworks. Herein, we summarize the progress in the development of “chiral reticular chemistry” through which a serial of homochiral or racemic reticular frameworks with novel topologies and functions can be targeted. To begin, we introduce the background of reticular chemistry and the potential of using chiral building blocks to assemble reticular frameworks, particularly MOFs. In the following section, we describe the synthetic diversity and complexity using enantiopure or racemic ligands and highlight the important role of enantiopurity engineering in affecting the ultimate products. To be more specific, we present (i) isotopological synthesis in which enantiopure or racemic ligands produce frameworks with the same net topology, where the racemic ligands form either racemic frameworks or conglomerates; (ii) intrinsically chiral net-dominated synthesis in which enantiopure or racemic ligands can form different underlying topologies or undergo distinct crystallization pathways; (iii) other atypical syntheses that typically come by way of serendipity, where the assembly mechanism is highly elusive (for example, the enantiomeric ligands of opposite chirality give rise to entirely different structures). Next, we discuss the applications of these unique reticular framework materials that are otherwise unachievable by conventional achiral materials or analogues, aiming to underline the unique role of chiral building blocks in reticular chemistry. Last, we point out future research directions of “chiral reticular chemistry”. Our Account aims to highlight the importance of chirality as a decisive parameter to control the ultimate structu","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"15 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143451825","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Functional Bis/Multimacrocyclic Materials Based on Cycloparaphenylene Carbon Nanorings","authors":"Xinyu Zhang, Youzhi Xu* and Pingwu Du*, ","doi":"10.1021/accountsmr.4c0033810.1021/accountsmr.4c00338","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00338https://doi.org/10.1021/accountsmr.4c00338","url":null,"abstract":"<p >Topologically unique nanocarbon materials with optoelectronic potential are both fascinating and challenging synthetic targets. Their distinctive molecular topologies often lead to chirality, unique optoelectronic properties, and encapsulation capabilities, stimulating advances in synthetic chemistry and materials science. The research on curved nanocarbon materials has garnered substantial interest due to the intricate relationship between their π-conjugation and molecular geometry, as well as their emerging applications in various fields. The introduction of curvature significantly affects the redox behaviors, optical properties, charge-transport capabilities, and self-assembly processes of these nanocarbon materials. The representative examples of curved aromatic systems are cycloparaphenylenes (CPPs) and related carbon nanorings. In these molecules, the nonplanar aromatic structures can induce unique radial π-conjugation and further endow them with distinctive photophysical properties. By adjusting the number of benzene rings in a CPP or incorporating diverse polycyclic aromatic hydrocarbon units, researchers can finely tune the optical and electronic properties of these nanostructures. Many potential applications can be discovered in the fields of fluorescent probes, organic light-emitting diodes (OLEDs), and optoelectronic devices. These properties establish CPP as an important scaffold to create novel carbon nanostructures. With the ongoing advancements in molecular topology, new opportunities are emerging within the fields of materials science, molecular electronics, and biomedicine. Given the exceptional electronic and photophysical properties of CPPs, there has been considerable interest in the development of topologically intriguing bis/multimacrocyclic architectures. It is anticipated that high dimensionality and unexplored topologies will endow these bis/multimacrocycles with unparalleled physical and chemical properties. This concise Account highlights recent developments from our research group on topologically functional materials based on CPP carbon nanorings, particularly their potential applications. Our discussion focuses on (i) the design and synthesis of a series of fully <i>sp</i><sup>2</sup>-hybridized all-benzenoid bismacrocycles, as well as [n]cycloparaphenylene-pillar[5]arene bismacrocycles; (ii) the construction of all-CPP-based long π-extended polymeric segments of the armchair SWCNT; and (iii) the synthesis of CPP-based mechanically interlocked molecules, specifically [12]CPP-[3]catenane. Structures like these CPP-based bis/multimacrocyclic architectures exhibit distinct properties─including radial π-conjugation, supramolecular properties, chirality, and unexpected dual-emissive and anti-Kasha photophysical characteristics due to their nonplanar geometries─that allow precise tuning of their HOMO–LUMO gap, emission profiles, and charge-transport behaviors. These properties make them promising for applications in O","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"6 4","pages":"399–410 399–410"},"PeriodicalIF":14.0,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143867463","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}