Pub Date : 2025-02-13DOI: 10.1016/j.chempr.2024.102403
Daliang Han , Feifei Wang , Quan-Hong Yang
Invitation of organic cosolvents into aqueous electrolytes has been widely proven effective in stabilizing zinc (Zn) anodes but easily brings about sluggish desolvation kinetics concurrently. In this issue of Chem, Geng and coworkers report an organic/aqueous hybrid electrolyte with an organic-solvent-free primary solvation sheath, achieving facile desolvation and durable Zn batteries under subzero conditions.
{"title":"Cold-resilient zinc batteries with organic-free solvation structures","authors":"Daliang Han , Feifei Wang , Quan-Hong Yang","doi":"10.1016/j.chempr.2024.102403","DOIUrl":"10.1016/j.chempr.2024.102403","url":null,"abstract":"<div><div>Invitation of organic cosolvents into aqueous electrolytes has been widely proven effective in stabilizing zinc (Zn) anodes but easily brings about sluggish desolvation kinetics concurrently. In this issue of <em>Chem</em>, Geng and coworkers report an organic/aqueous hybrid electrolyte with an organic-solvent-free primary solvation sheath, achieving facile desolvation and durable Zn batteries under subzero conditions.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 2","pages":"Article 102403"},"PeriodicalIF":19.1,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142987278","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}
Pub Date : 2025-02-13DOI: 10.1016/j.chempr.2025.102452
Elad Harel
In their recent work published in the Journal of the American Chemical Society, Zhang et al. introduce a novel approach combining electron diffraction data with computational optimization to derive high-resolution atomic structures of covalent organic frameworks (COFs). This breakthrough demonstrates the transformative potential of integrating computational and statistical tools with experimental datasets, paving the way for innovative COF design and discovery.
{"title":"From low-res measurements to high-res insights: Revolutionizing COF structural determination","authors":"Elad Harel","doi":"10.1016/j.chempr.2025.102452","DOIUrl":"10.1016/j.chempr.2025.102452","url":null,"abstract":"<div><div>In their recent work published in the <em>Journal of the American Chemical Society</em>, Zhang et al. introduce a novel approach combining electron diffraction data with computational optimization to derive high-resolution atomic structures of covalent organic frameworks (COFs). This breakthrough demonstrates the transformative potential of integrating computational and statistical tools with experimental datasets, paving the way for innovative COF design and discovery.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 2","pages":"Article 102452"},"PeriodicalIF":19.1,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143072280","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}
Pub Date : 2025-02-13DOI: 10.1016/j.chempr.2024.10.007
Wanying Han , Longfei Lin , Ziyu Cen , Yubin Ke , Qian Xu , Junfa Zhu , Xuelei Mei , Zhanghui Xia , Xinrui Zheng , Yaqin Wang , Yani Liu , Mingyuan He , Haihong Wu , Buxing Han
Chemical upcycling of polyethylene (PE) waste presents a viable and promising approach to address the issues of plastic waste accumulation. However, developing cost-effective and efficient routes for converting PE waste into value-added products remains a challenging task. Here, we report a one-pot, dual-catalyst system for efficient conversion of PE into gasoline without the need for noble-metal catalysts, external hydrogen, or solvents. A gasoline yield of up to 87% is achieved over a dual-catalyst system comprising WZr-KIT-6 and HZSM-5 at 240°C. The WZr-KIT-6 catalyst facilitated the activation and pre-cracking of PE chains into unsaturated oligomers over Si-O-Zr and W-O(H)-Zr sites. These unsaturated oligomers, characterized by increased mobility and reactivity, were subsequently converted into C4–C12 gasoline-range compounds through β-scission, isomerization, and hydride transfer over HZSM-5. The synergistic reaction mechanism over mesoporous and microporous materials was crucial for enhancing the efficiency and selectivity of PE conversion.
{"title":"One-pot catalytic conversion of polyethylene wastes to gasoline through a dual-catalyst system","authors":"Wanying Han , Longfei Lin , Ziyu Cen , Yubin Ke , Qian Xu , Junfa Zhu , Xuelei Mei , Zhanghui Xia , Xinrui Zheng , Yaqin Wang , Yani Liu , Mingyuan He , Haihong Wu , Buxing Han","doi":"10.1016/j.chempr.2024.10.007","DOIUrl":"10.1016/j.chempr.2024.10.007","url":null,"abstract":"<div><div>Chemical upcycling of polyethylene (PE) waste presents a viable and promising approach to address the issues of plastic waste accumulation. However, developing cost-effective and efficient routes for converting PE waste into value-added products remains a challenging task. Here, we report a one-pot, dual-catalyst system for efficient conversion of PE into gasoline without the need for noble-metal catalysts, external hydrogen, or solvents. A gasoline yield of up to 87% is achieved over a dual-catalyst system comprising WZr-KIT-6 and HZSM-5 at 240°C. The WZr-KIT-6 catalyst facilitated the activation and pre-cracking of PE chains into unsaturated oligomers over Si-O-Zr and W-O(H)-Zr sites. These unsaturated oligomers, characterized by increased mobility and reactivity, were subsequently converted into C<sub>4</sub>–C<sub>12</sub> gasoline-range compounds through β-scission, isomerization, and hydride transfer over HZSM-5. The synergistic reaction mechanism over mesoporous and microporous materials was crucial for enhancing the efficiency and selectivity of PE conversion.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 2","pages":"Article 102340"},"PeriodicalIF":19.1,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142589051","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}
Pub Date : 2025-02-13DOI: 10.1016/j.chempr.2025.102412
Zirui Gao , Shixiang Yu , Zeyan Cen , Ding Ma
In a recent Cell Reports Sustainability article, Bajada et al. compare the different catalytic systems in fine chemical manufacturing based on cost and greenhouse gas emissions.1 They conclude that the adoption of heterogeneous single-atom catalysts (SACs)2 over traditional homogeneous systems is critical for the development of sustainable catalysis.
{"title":"The sustainability potential of single-atom catalysts in chemical process","authors":"Zirui Gao , Shixiang Yu , Zeyan Cen , Ding Ma","doi":"10.1016/j.chempr.2025.102412","DOIUrl":"10.1016/j.chempr.2025.102412","url":null,"abstract":"<div><div>In a recent <em>Cell Reports Sustainability</em> article, Bajada et al. compare the different catalytic systems in fine chemical manufacturing based on cost and greenhouse gas emissions.<span><span><sup>1</sup></span></span> They conclude that the adoption of heterogeneous single-atom catalysts (SACs)<span><span><sup>2</sup></span></span> over traditional homogeneous systems is critical for the development of sustainable catalysis.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 2","pages":"Article 102412"},"PeriodicalIF":19.1,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143044242","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}
Pub Date : 2025-02-13DOI: 10.1016/j.chempr.2024.09.015
Federico Villalobos , Jan Berger , Adam Matěj , Reed Nieman , Ana Sánchez-Grande , Diego Soler , Andrés Pinar Solé , Hans Lischka , Mikuláš Matoušek , Jiri Brabec , Libor Veis , Alba Millan , Carlos Sánchez-Sánchez , Araceli G. Campaña , Juan M. Cuerva , Pavel Jelínek
Molecular π-magnets based on single organic molecules have attracted increasing attention for their potential applications in optoelectronics and spintronics. Global aromaticity in conjugated macrocyclic polyradicaloids is still an open question that has only been tackled in molecules with an even number of electrons. Here, we report the on-surface synthesis of a cyclopenta-ring-fused oligo(m-phenylene) macrocycle, 9MC, with an odd number of electrons. The generated polyradicaloid undergoes a surface-induced distortion to a D3h symmetry with a fully delocalized doublet ground state. Interestingly, 9MC exhibits two aromatic annulene-within-an-annulene (AWA) ring currents in the inner and outer rings.
{"title":"Globally aromatic odd-electron π-magnetic macrocycle","authors":"Federico Villalobos , Jan Berger , Adam Matěj , Reed Nieman , Ana Sánchez-Grande , Diego Soler , Andrés Pinar Solé , Hans Lischka , Mikuláš Matoušek , Jiri Brabec , Libor Veis , Alba Millan , Carlos Sánchez-Sánchez , Araceli G. Campaña , Juan M. Cuerva , Pavel Jelínek","doi":"10.1016/j.chempr.2024.09.015","DOIUrl":"10.1016/j.chempr.2024.09.015","url":null,"abstract":"<div><div>Molecular π-magnets based on single organic molecules have attracted increasing attention for their potential applications in optoelectronics and spintronics. Global aromaticity in conjugated macrocyclic polyradicaloids is still an open question that has only been tackled in molecules with an even number of electrons. Here, we report the on-surface synthesis of a cyclopenta-ring-fused oligo(<em>m</em>-phenylene) macrocycle, <strong>9MC</strong>, with an odd number of electrons. The generated polyradicaloid undergoes a surface-induced distortion to a <em>D</em><sub><em>3</em>h</sub> symmetry with a fully delocalized doublet ground state. Interestingly, <strong>9MC</strong> exhibits two aromatic annulene-within-an-annulene (AWA) ring currents in the inner and outer rings.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 2","pages":"Article 102316"},"PeriodicalIF":19.1,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142436152","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}
Pub Date : 2025-02-13DOI: 10.1016/j.chempr.2024.10.008
Linh Duy Thai , Jochen A. Kammerer , Dmitri Golberg , Hatice Mutlu , Christopher Barner-Kowollik
The installation of stimuli-responsive moieties into their main chain maximizes the stimuli response of polymers. Yet, facile and orthogonal synthesis of such complex macromolecules is a daunting challenge, especially for achieving absolute chain-end-group fidelity, monodispersity, and the formation of block copolymers (BCPs). We harness metal-free hydroxyl-yne click and deprotection chemistry to realize monodisperse, sequence-defined oligomers and BCPs featuring α-bisimines as main-chain photoswitches and orthogonally incorporate functional terminal groups (olefins, acrylates, and non-activated alkynes). We reveal the significant influence of the sequence on solution and solid-state material properties, which manifests as a strong odd-even effect on the hydrodynamic volume, glass transition temperature, and BCP domain spacing. The odd-even effect originates from the distinct symmetries of the sequences resulting from our precise synthetic strategy. Thus, our sequence-defined, orthogonal synthesis strategy with near absolute chain-end-group fidelity and wide functional group compatibility paves the way toward complex polymeric materials with precise properties, topology, composition, and main-chain functionalities.
{"title":"Sequence-defined main-chain photoswitching macromolecules with odd-even-effect-controlled properties","authors":"Linh Duy Thai , Jochen A. Kammerer , Dmitri Golberg , Hatice Mutlu , Christopher Barner-Kowollik","doi":"10.1016/j.chempr.2024.10.008","DOIUrl":"10.1016/j.chempr.2024.10.008","url":null,"abstract":"<div><div>The installation of stimuli-responsive moieties into their main chain maximizes the stimuli response of polymers. Yet, facile and orthogonal synthesis of such complex macromolecules is a daunting challenge, especially for achieving absolute chain-end-group fidelity, monodispersity, and the formation of block copolymers (BCPs). We harness metal-free hydroxyl-yne click and deprotection chemistry to realize monodisperse, sequence-defined oligomers and BCPs featuring α-bisimines as main-chain photoswitches and orthogonally incorporate functional terminal groups (olefins, acrylates, and non-activated alkynes). We reveal the significant influence of the sequence on solution and solid-state material properties, which manifests as a strong odd-even effect on the hydrodynamic volume, glass transition temperature, and BCP domain spacing. The odd-even effect originates from the distinct symmetries of the sequences resulting from our precise synthetic strategy. Thus, our sequence-defined, orthogonal synthesis strategy with near absolute chain-end-group fidelity and wide functional group compatibility paves the way toward complex polymeric materials with precise properties, topology, composition, and main-chain functionalities.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 2","pages":"Article 102341"},"PeriodicalIF":19.1,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142574648","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}
Pub Date : 2025-02-13DOI: 10.1016/j.chempr.2024.10.024
Ruozhou Huang , Yuping Wang
In a recent issue of Chem, an innovative approach for the synthesis of crystalline [2]catenane-containing covalent organic frameworks was developed. This breakthrough elucidates how the dynamics of microscopic, interlocked components influence material properties, thereby advancing the design of two-dimensional materials with sophisticated topological features.
{"title":"Ordered [2]catenanes in covalent organic frameworks: From molecules to materials","authors":"Ruozhou Huang , Yuping Wang","doi":"10.1016/j.chempr.2024.10.024","DOIUrl":"10.1016/j.chempr.2024.10.024","url":null,"abstract":"<div><div>In a recent issue of <em>Chem</em>, an innovative approach for the synthesis of crystalline [2]catenane-containing covalent organic frameworks was developed. This breakthrough elucidates how the dynamics of microscopic, interlocked components influence material properties, thereby advancing the design of two-dimensional materials with sophisticated topological features.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 2","pages":"Article 102357"},"PeriodicalIF":19.1,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142760252","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}
The practical application of Zn-based batteries is compromised by rampant dendrite growth, unfavorable side reactions, and serious capacity decay. We report a trifunctional glutarimide (Glu) electrolyte additive to stabilize the electrochemical reaction of the Zn anode and facilitate redox activity of the cathode. Theoretical calculations and spectroscopic characterizations reveal that Glu with the electron-withdrawing/donating capability can substitute partially coordinated water and manipulate the solvation structure by reinforced ion-dipole interactions. Meanwhile, Glu can form a solid electrolyte interphase layer and alleviate parasitic reactions. Consequently, Glu renders excellent Zn plating/stripping cycling of 2,000 h at 1 mA cm−2/1 mAh cm−2. Even at an ultra-high depth of discharge of 85.2%, a stable cycling of 138 h is obtained. The formulated additive serves as the charge redistributor and decouples the cation-anion interaction to stabilize the interaction of ClO4− with the half-oxidized protonated polyaniline, enabling the Zn-organic battery with enhanced energy storage performance.
{"title":"Ion-dipole interaction manipulated bilateral interface chemistry for deep rechargeability and high redox activity of Zn-organic batteries","authors":"Yanyan Chen, Bowen Yin, Yinxiang Zeng, Hongfei Wang, Bin-Bin Xie, Deyan Luan, Yong Hu, Xiong Wen (David) Lou","doi":"10.1016/j.chempr.2025.102411","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102411","url":null,"abstract":"The practical application of Zn-based batteries is compromised by rampant dendrite growth, unfavorable side reactions, and serious capacity decay. We report a trifunctional glutarimide (Glu) electrolyte additive to stabilize the electrochemical reaction of the Zn anode and facilitate redox activity of the cathode. Theoretical calculations and spectroscopic characterizations reveal that Glu with the electron-withdrawing/donating capability can substitute partially coordinated water and manipulate the solvation structure by reinforced ion-dipole interactions. Meanwhile, Glu can form a solid electrolyte interphase layer and alleviate parasitic reactions. Consequently, Glu renders excellent Zn plating/stripping cycling of 2,000 h at 1 mA cm<sup>−2</sup>/1 mAh cm<sup>−2</sup>. Even at an ultra-high depth of discharge of 85.2%, a stable cycling of 138 h is obtained. The formulated additive serves as the charge redistributor and decouples the cation-anion interaction to stabilize the interaction of ClO<sub>4</sub><sup>−</sup> with the half-oxidized protonated polyaniline, enabling the Zn-organic battery with enhanced energy storage performance.","PeriodicalId":268,"journal":{"name":"Chem","volume":"50 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143401696","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}
Pub Date : 2025-02-13DOI: 10.1016/j.chempr.2024.09.006
Thirumurugan Prakasam , Sudhir Kumar Sharma , Florent Ravaux , Farah Benyettou , Matteo Lusi , Varghese Sabu , Philippe Bazin , Thomas Delclos , Ramesh Jagannathan , Jamie Whelan , Mohamad El-Roz , Mark A. Olson , Mahmoud Abdellatief , Obieda S. Mudraj , Felipe Gándara , Ali Trabolsi
Molecular-level structural modification is a well-established approach to impart advanced functionality to materials that continues to be the focus of research and development in both academic and industrial laboratories. Here, we report the synthesis of an ordered two-dimensional (2D) poly[2]catenate from the simultaneous self-assembly of two organic ligands and a metal salt by the formation of catenate links using metal coordination and imine condensation reactions. Subsequent chemical reduction of the imine bonds generated the corresponding demetallized poly[2]catenane, which was found to have greater non-rigid-body-like character than the poly[2]catenate as a result of the increased internal dynamics of the mechanical bonds and resulted in an 8-fold increase in elasticity. This synthetic approach allowed for the efficient incorporation of mechanically interlocked molecules (MIMs) within a 2D ordered structure and demonstrated their importance in improving the physical properties of materials by accessing molecular degrees of freedom that cannot be achieved by other means.
{"title":"2D covalent organic framework via catenation","authors":"Thirumurugan Prakasam , Sudhir Kumar Sharma , Florent Ravaux , Farah Benyettou , Matteo Lusi , Varghese Sabu , Philippe Bazin , Thomas Delclos , Ramesh Jagannathan , Jamie Whelan , Mohamad El-Roz , Mark A. Olson , Mahmoud Abdellatief , Obieda S. Mudraj , Felipe Gándara , Ali Trabolsi","doi":"10.1016/j.chempr.2024.09.006","DOIUrl":"10.1016/j.chempr.2024.09.006","url":null,"abstract":"<div><div>Molecular-level structural modification is a well-established approach to impart advanced functionality to materials that continues to be the focus of research and development in both academic and industrial laboratories. Here, we report the synthesis of an ordered two-dimensional (2D) poly[2]catenate from the simultaneous self-assembly of two organic ligands and a metal salt by the formation of catenate links using metal coordination and imine condensation reactions. Subsequent chemical reduction of the imine bonds generated the corresponding demetallized poly[2]catenane, which was found to have greater non-rigid-body-like character than the poly[2]catenate as a result of the increased internal dynamics of the mechanical bonds and resulted in an 8-fold increase in elasticity. This synthetic approach allowed for the efficient incorporation of mechanically interlocked molecules (MIMs) within a 2D ordered structure and demonstrated their importance in improving the physical properties of materials by accessing molecular degrees of freedom that cannot be achieved by other means.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 2","pages":"Article 102307"},"PeriodicalIF":19.1,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142384025","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}
Pub Date : 2025-02-13DOI: 10.1016/j.chempr.2024.11.009
Zhu Zhuo , Zi-Ang Nan , Wen-Zheng Fu , Wei Wang , Guo-Ling Li , Ming-Yan Wu , Maochun Hong , You-Gui Huang
Constructing artificial sophisticated architectures from simple small-molecular subunits by cooperative interactions remains one of the most formidable challenges. Herein, we report a complex supramolecular structure, {{[CoL(SCN)]20}{[CoL(SCN)]24}3(SO4)23(HSO4)46}·246(CH3CN) (1), that arises from the assembly of [CoL(SCN)]+ with SO42− and HSO4− (L = tris(2-benzimidazolylmethyl)amine) under solvothermal condition. The crystallization of compound 1 is driven by the cooperation of the π-π stacking interactions between [CoL(SCN)]+ cations and the hydrogen bonds between [CoL(SCN)]+ and SO42− and HSO4−. [CoL(SCN)]+ cations self-associate through intermolecular π-π stacking interactions to create two π-stacked polyhedral 512-{[CoL(SCN)]20} dodecahedra and 51262-{[CoL(SCN)]24} tetrakaidekahedra. These two π-stacked polyhedral subunits coexist in the same lattice in a 1:3 ratio and coordinate with SO42− and HSO4−, resulting in a complex Frank-Kasper (FK) A15 structure. This research demonstrates that small-molecular scaffolds can assemble into sophisticated architectures and creates exciting perspectives for constructing sophisticated clathrate structures from simple small molecules.
{"title":"Anion-coordination- and π-π-stacking-interaction-driven assembly of a complex Frank-Kasper structure","authors":"Zhu Zhuo , Zi-Ang Nan , Wen-Zheng Fu , Wei Wang , Guo-Ling Li , Ming-Yan Wu , Maochun Hong , You-Gui Huang","doi":"10.1016/j.chempr.2024.11.009","DOIUrl":"10.1016/j.chempr.2024.11.009","url":null,"abstract":"<div><div>Constructing artificial sophisticated architectures from simple small-molecular subunits by cooperative interactions remains one of the most formidable challenges. Herein, we report a complex supramolecular structure, {{[CoL(SCN)]<sub>20</sub>}{[CoL(SCN)]<sub>24</sub>}<sub>3</sub>(SO<sub>4</sub>)<sub>23</sub>(HSO<sub>4</sub>)<sub>46</sub>}·246(CH<sub>3</sub>CN) (<strong>1</strong>), that arises from the assembly of [CoL(SCN)]<sup>+</sup> with SO<sub>4</sub><sup>2−</sup> and HSO<sub>4</sub><sup>−</sup> (L = tris(2-benzimidazolylmethyl)amine) under solvothermal condition. The crystallization of compound <strong>1</strong> is driven by the cooperation of the <em>π-π</em> stacking interactions between [CoL(SCN)]<sup>+</sup> cations and the hydrogen bonds between [CoL(SCN)]<sup>+</sup> and SO<sub>4</sub><sup>2−</sup> and HSO<sub>4</sub><sup>−</sup>. [CoL(SCN)]<sup>+</sup> cations self-associate through intermolecular <em>π-π</em> stacking interactions to create two <em>π</em>-stacked polyhedral 5<sup>12</sup>-{[CoL(SCN)]<sub>20</sub>} dodecahedra and 5<sup>12</sup>6<sup>2</sup>-{[CoL(SCN)]<sub>24</sub>} tetrakaidekahedra. These two <em>π</em>-stacked polyhedral subunits coexist in the same lattice in a 1:3 ratio and coordinate with SO<sub>4</sub><sup>2−</sup> and HSO<sub>4</sub><sup>−</sup>, resulting in a complex Frank-Kasper (FK) A15 structure. This research demonstrates that small-molecular scaffolds can assemble into sophisticated architectures and creates exciting perspectives for constructing sophisticated clathrate structures from simple small molecules.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 2","pages":"Article 102371"},"PeriodicalIF":19.1,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832715","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}
扫码关注我们
求助内容：
应助结果提醒方式：
京公网安备 11010802042870号