Chemical Science最新文献_第8页

Ultra-high resolution magnetic resonance microscopy of in situ gadolinium gold nanoparticle-labeled cells in the rat brain 大鼠脑内纳米钆金标记细胞的超高分辨率磁共振显微镜观察

IF 8.4 1区化学

Chemical Science Pub Date : 2025-06-03 DOI: 10.1039/d5sc01588j

Alena Kisel, Minrui Luo, Matthew D. Bailey, Harman Ghuman, Matthew Rotz, Vinícius P. Campos, Marcelo A. C. Vieira, T. Kevin Hitchens, Thomas J. Meade, Michel Modo

{"title":"Ultra-high resolution magnetic resonance microscopy of in situ gadolinium gold nanoparticle-labeled cells in the rat brain","authors":"Alena Kisel, Minrui Luo, Matthew D. Bailey, Harman Ghuman, Matthew Rotz, Vinícius P. Campos, Marcelo A. C. Vieira, T. Kevin Hitchens, Thomas J. Meade, Michel Modo","doi":"10.1039/d5sc01588j","DOIUrl":"https://doi.org/10.1039/d5sc01588j","url":null,"abstract":"Mapping the distribution of cells within a tissue using MR imaging has remained a significant challenge for the field. Cellular MRI can trace cells within tissue, but typically does not achieve the resolution necessary to define a cell's precise anatomical location. To detect cells with ultra-high resolution MRI, a high r1 relaxivity intracellular contrast agent is required. Localizing this contrast within its biological context also necessitates an isotropic spatial resolution corresponding to the size of a cell's cytoplasm (∼20 μm) to place it within its biological context. We here demonstrate that gadolinium gold nanoparticles (GdAuNP) induce a high T1-weighted cellular MRI contrast at ultra-high magnetic fields (9.4 T, and 11.7 T) that affords in situ labelled cell detection at very high resolutions (150, 100, 50, and 20 μm). A 20 μm 3D gradient-echo image (400 minutes scan) combined with MR image denoising robustly visualized the distribution of in situ labeled cells in the rat brain. Signal averaging (NA = 5) also consistently afforded the detection of labeled cells. Positive T1-weighted contrast was confirmed to be caused by GdAuNP using histology. Immunohistochemistry confirmed the presence of GdAuNP almost entirely inside cells, primarily those of the neuronal lineage. Histology verified that the MR images accurately visualized individual cells' distribution within their anatomical context. Cellular resolution MRI of GdAuNP-labeled cells hence affords new avenues to investigate how individual cells contribute to the development, repair, and regeneration of tissues.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"54 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144201753","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}

引用次数: 0

Lithium-Ion Conducting Self-Assembled Organic Nanowires: Optimizing Mechanical Performance and Ionic Conductivity through Programmable Supramolecular Interactions. 锂离子导电自组装有机纳米线：通过可编程超分子相互作用优化机械性能和离子电导率。

IF 8.4 1区化学

Chemical Science Pub Date : 2025-06-03 DOI: 10.1039/d5sc00159e

Vishwakarma Ravikumar Ramlal, Sam Sankar Selvasundarasekar, Akanksha Singh, Jenil Ankola, Rabindranath Lo, Subtrata Kundu, Amal Kumar Mandal

{"title":"Lithium-Ion Conducting Self-Assembled Organic Nanowires: Optimizing Mechanical Performance and Ionic Conductivity through Programmable Supramolecular Interactions.","authors":"Vishwakarma Ravikumar Ramlal, Sam Sankar Selvasundarasekar, Akanksha Singh, Jenil Ankola, Rabindranath Lo, Subtrata Kundu, Amal Kumar Mandal","doi":"10.1039/d5sc00159e","DOIUrl":"https://doi.org/10.1039/d5sc00159e","url":null,"abstract":"Abstract\u0000: The emergence of wearable devices has led to a greater need for battery materials that are safe, resilient, exhibit high levels of ionic conductivity. Here, we present a supramolecular design as a useful tactic through fine tuning of the noncovalent interactions to overcome the standard trade-off in solid state Li-ion conductors between ionic conductivity and mechanical resilience. We report solution processable self-assembled organic nanowires (SONs) with varying supramolecular interactions through structural mutation to boost Li-ion conductivity and mechanical integrity. The findings indicate that precise H-bonding plays a crucial role in achieving a maximum Young's modulus (1050.5 ± 38 MPa), and toughness (15666 ± 423 kJ/m3), surpassing the impact of the number of H-bonding sites. Highly structured H-bonded morphology facilitated the creation of binding pockets, enhancing lithiation, in achieving the highest ionic conductivity (3.12 × 10-4 Scm-1) with Li-ion transference number of 0.8 at 298 K. The molecular dynamics simulation demonstrates that, among the various interaction sites, the hopping of Li-ions through the axial pathway is favoured over the planar pathway. This study represents a pioneering example illustrating the methodology behind the impact of noncovalent interactions within nanoscale assemblies on the ion conductivity and mechanical characteristics of supramolecular Li-ion conductors.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"99 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144201755","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}

引用次数: 0

High-capacity aqueous imidazolium-ion battery enabled by MMZ-H+/H+ co-intercalation in a near neutral electrolyte 在接近中性的电解质中通过MMZ-H+/H+共插层实现高容量咪唑水离子电池

IF 8.4 1区化学

Chemical Science Pub Date : 2025-06-03 DOI: 10.1039/d5sc02677f

Haiping Yu, Zhihui Wang, Mengxiao Li, Mingjun Hu, Jun Yang, Rui Li, Bei Wang, Guoqing Zhao, Xinyu Wang, Xiaorong Yan, Yuxin Hao, Huige Ma, Jingru Liu

{"title":"High-capacity aqueous imidazolium-ion battery enabled by MMZ-H+/H+ co-intercalation in a near neutral electrolyte","authors":"Haiping Yu, Zhihui Wang, Mengxiao Li, Mingjun Hu, Jun Yang, Rui Li, Bei Wang, Guoqing Zhao, Xinyu Wang, Xiaorong Yan, Yuxin Hao, Huige Ma, Jingru Liu","doi":"10.1039/d5sc02677f","DOIUrl":"https://doi.org/10.1039/d5sc02677f","url":null,"abstract":"Rechargeable aqueous batteries are regarded as promising candidates for large-scale energy storage with the advantages of cost-effectiveness, environmentally friendliness, and innate safety. However, to date, most of the aqueous ion batteries that have been reported are equipped with metal cation charge carriers and encounter either poor sustainability or low reaction activity. Here, we first reported an aqueous imidazolium-ion battery with MMZ-H+/H+ as co-intercalated ions. In detail, we configured an almost neutral electrolyte with a wide electrochemical window of 2.66 V by adding an appropriate amount of alkaline 1-methylimidazole (MMZ) to 0.5 M H2SO4, named as 50M-10S electrolyte. Due to the strong binding energy between MMZ and H+, the MMZ-H+ as an entire unit can insert into or extract from HATN-3CN (hexaazatrinaphthalene-2,8,14-tricarbonitrile) electrode. The MMZ-H+ and H+ co-insertion increases the capacity by 40% compared to pure H+ insertion in this proton battery (287.6 mAh g-1 in 50M-10S electrolyte vs. 206.8 mAh g-1 in 0.5 M H2SO4 electrolyte, 0.1 A g-1). Theoretical calculations illustrated that the insertion of MMZ-H+ can further activate the unreacted N active sites due to their enhanced nucleophilicity derived from stronger electron-donating ability of ionized nitrogen sites than the protonated one. Moreover, the assembled full batteries also exhibit ultra-high specific capacity (266.6 mAh g-1, 1 A g-1) and ultra-slow degradation (capacity retention of 97 %, 1 A g-1, 1000 cycles). This research further enriches the library of inserted ions and will help to understand and enhance proton storage in near-neutral electrolytes and build new battery model.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"169 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144202092","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}

引用次数: 0

Thermodynamic insights into the self-assembly of zeolitic imidazolate frameworks from computer simulations 从计算机模拟的热力学见解到沸石咪唑盐框架的自组装

IF 8.4 1区化学

Chemical Science Pub Date : 2025-06-03 DOI: 10.1039/d5sc00807g

Emilio Méndez, Rocio Semino

{"title":"Thermodynamic insights into the self-assembly of zeolitic imidazolate frameworks from computer simulations","authors":"Emilio Méndez, Rocio Semino","doi":"10.1039/d5sc00807g","DOIUrl":"https://doi.org/10.1039/d5sc00807g","url":null,"abstract":"New metal–organic frameworks (MOFs) are periodically synthesized all over the world due to the wide range of societally and environmentally relevant applications they possess. However, the mechanisms and thermodynamics associated with MOF self-assembly are poorly understood because of the difficulties in studying such a multi-scale process with molecular-level resolution. In this work, we performed well-tempered metadynamics simulations of the early nucleation and late growth steps of the self-assembly of ZIF-4 using a partially reactive force field. We found that the formation of building blocks is a complex, multi-step process that involves changes in the coordination of the metal ion. Saturating the ligand coordination of a metal ion is more energetically favorable during growth than during early formation of building blocks. The addition of a fourth ligand is less exergonic than it is for the first three and the associated free energy is highly dependent on the local environment of the undercoordinated metal ion. The stability of this bond depends on the strength of the solvent–metal ion interaction. Incorporating a ligand to a ZIF-1 crystal is less favorable compared to the more stable ZIF-4 polymorph. Milder differences were found when comparing the growth of (100), (010) and (001) ZIF-4 surfaces.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"15 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144201752","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}

引用次数: 0

Access to amidines via C(sp²)-N coupling of trifluoroborate-iminiums with N-fluorobenzenesulfonimide. 通过三氟硼酸盐与n -氟苯磺酰亚胺的C(sp2)-N偶联获得脒。

IF 7.6 1区化学

Chemical Science Pub Date : 2025-06-03 DOI: 10.1039/d5sc02912k

Damijan Knez, Andrej Šterman, Izidor Sosič, Franc Perdih, Gonzalo D Nuñez, Tilen Knaflič, Denis Arčon, Maria Besora, Jorge J Carbó, Elena Fernández, Zdenko Časar

{"title":"Access to amidines via C(sp2)-N coupling of trifluoroborate-iminiums with N-fluorobenzenesulfonimide.","authors":"Damijan Knez, Andrej Šterman, Izidor Sosič, Franc Perdih, Gonzalo D Nuñez, Tilen Knaflič, Denis Arčon, Maria Besora, Jorge J Carbó, Elena Fernández, Zdenko Časar","doi":"10.1039/d5sc02912k","DOIUrl":"10.1039/d5sc02912k","url":null,"abstract":"Amidines are an important class of organic compounds with widespread application as superbases, nucleophilic catalysts, and building blocks of heterocyclic compounds in organic synthesis. Moreover, they represent an important structural motif in medicinal chemistry. This work describes an application of primary trifluoroborate-iminiums in unprecedented azide- and transition-metal-free transformation to N-sulfonyl amidines in the presence of N-fluorobenzenesulfonimide (NFSI). This novel C(sp2)-N bond-forming reaction proceeds without excess of any reagent, under mild conditions and provides good to high yields of N-sulfonyl amidines by a simple isolation procedure. Density functional theory (DFT) mechanistic studies into this novel transformation support that the use of a base is required to activate either the trifluoroborate-iminium or the NFSI and promote the C(sp2)-N bond formation via nucleophilic attack of the nitrogen. The utility of the developed methodology is showcased with the synthesis of two bioactive compounds.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":7.6,"publicationDate":"2025-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12132563/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144224444","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}

引用次数: 0

Mass spectrometric Imaging of Organic and Metallic Metabolites by Plasmon-Induced Interfacial Charge-Transfer Transition （PICTT）on Au Sputtered ITO Slides 等离子体诱导界面电荷转移跃迁（PICTT）在Au溅射ITO载玻片上的有机和金属代谢物质谱成像

IF 8.4 1区化学

Chemical Science Pub Date : 2025-06-02 DOI: 10.1039/d5sc02632f

Hongying Zhong, Shao Chang, Xin Zhou, Anji Gao, Yixiang Luo, Yujia Linhui Shan, Lin Zhang, Zhengwei Gui, Xingchen Huang, Xiaoyuan Hu, Tianci Huo, Linhui Liu

{"title":"Mass spectrometric Imaging of Organic and Metallic Metabolites by Plasmon-Induced Interfacial Charge-Transfer Transition （PICTT）on Au Sputtered ITO Slides","authors":"Hongying Zhong, Shao Chang, Xin Zhou, Anji Gao, Yixiang Luo, Yujia Linhui Shan, Lin Zhang, Zhengwei Gui, Xingchen Huang, Xiaoyuan Hu, Tianci Huo, Linhui Liu","doi":"10.1039/d5sc02632f","DOIUrl":"https://doi.org/10.1039/d5sc02632f","url":null,"abstract":"Protonation/deprotonation is the major ionization mechanism of organic molecules in current electrospray ionization (ESI) and matrix assisted laser desorption ionization mass spectrometric (MALDI MS) imaging. But cellular complexities are far beyond protonated or deprotonated organic molecules. There are tremendous endogenous organic and metallic metabolites that regulate oxidization-reduction homeostasis cannot be protonated or deprotonated. We describe an electron-driven ionization paradigm for mass spectrometric imaging of organic and metallic metabolites based on the charge and energy flow at the plasmonic metal-molecule interface. Enhanced plasmonic electron transfer was observed on Au sputtered ITO glass slides that were made with a physical vapor deposition approach. Plasmon-induced interfacial charge-transfer transition (PICTT) enables the decay of plasmons by direct excitation of electrons from Au atoms to strongly coupled electron receptors in tissues sections that are blotted on Au sputtered ITO slides. The highly reactive plasmonic hot electrons facilitates not only the mass spectrometric imaging of endogenous organic metabolites, but also the in-situ surface plasmon-driven chemical reactions that can generate coordinative species for the visualization of endogenous metal ions. Beyond the biological application, the PICTT MS technique provides a way to tackle with the nature of the electronic excitations at the plasmon–molecule interface that has been challenging because of the lack of suitable experimental tool to directly monitor the outcomes of the interaction of the electron with an adsorbate.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"9 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-06-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144201757","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}

引用次数: 0

Iron-Assisted Growth of Anisotropic ZnO Nanostructures 各向异性ZnO纳米结构的铁辅助生长

IF 8.4 1区化学

Chemical Science Pub Date : 2025-06-02 DOI: 10.1039/d5sc01974e

Zhengxi Xuan, Avisek Dutta, Shuo Liu, Yueling Qin, Kaiwen Chen, Zheng Fu, Paras N. Prasad, Chaochao Dun, Mark T. Swihart

{"title":"Iron-Assisted Growth of Anisotropic ZnO Nanostructures","authors":"Zhengxi Xuan, Avisek Dutta, Shuo Liu, Yueling Qin, Kaiwen Chen, Zheng Fu, Paras N. Prasad, Chaochao Dun, Mark T. Swihart","doi":"10.1039/d5sc01974e","DOIUrl":"https://doi.org/10.1039/d5sc01974e","url":null,"abstract":"Anisotropic nanostructures offer a promising pathway to modulate structure-function relationships of materials. However, the correlation between growth direction of high-quality anisotropic nanostructures, the synthesis conditions and mechanisms controlling their growth, and their magnetic and optical properties remain underexplored. In this study, we developed an iron-assisted anisotropic growth method to form zinc oxide nanostructures on the O-polar (000-1) surface, resulting in two distinct ZnO-based nanostructures: hand-shaped nanostructures and truncated hexagonal nanopyramids. In contrast to most reports of anisotropic nanostructure synthesis, which primarily focus on morphology control through ligand-ligand interactions, the current study probes the effects of doping on anisotropic growth, and how doping, along with ligand-ligand interactions and facet-specific ligand binding, control nanostructure morphology. The reaction mechanisms leading to formation of these novel structures were thoroughly probed by systematically manipulating synthesis parameters. A two-step formation mechanism was identified: first, a hexagonal platform forms through an initial homogeneous nucleation process, followed by secondary heterogeneous nucleation, which results in metastable secondary nanostructures growing on the oxygen-rich template. Optical and magnetic properties of these Fe/ZnO nanostructures were characterized. Our findings provide a new strategy that uses a magnetic element as a dopant to build new nanostructures with ZnO of controllable size and shape growing on an oxygen-rich crystal plane. These materials could have applications in novel technologies where both optoelectronic and magnetic properties are of interest.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"103 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-06-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144192833","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}

引用次数: 0

Shape sorting of two distinct amino acid residues at the multiple binding sites of a porous metal-macrocycle framework 多孔金属-大环骨架多结合位点上两种不同氨基酸残基的形状分选

IF 8.4 1区化学

Chemical Science Pub Date : 2025-06-02 DOI: 10.1039/d5sc00795j

Shohei Tashiro, Kosuke Nakata, Ryunosuke Hayashi, Mitsuhiko Shionoya

{"title":"Shape sorting of two distinct amino acid residues at the multiple binding sites of a porous metal-macrocycle framework","authors":"Shohei Tashiro, Kosuke Nakata, Ryunosuke Hayashi, Mitsuhiko Shionoya","doi":"10.1039/d5sc00795j","DOIUrl":"https://doi.org/10.1039/d5sc00795j","url":null,"abstract":"The arrangement of amino acids within crystalline porous materials represents a unique approach to enhance their functionalities such as catalysis, separation and sensing. In particular, the simultaneous arrangement of distinct residues in crystalline frameworks, i.e., shape sorting, remains one of the most important challenges. Here, we demonstrate the shape sorting of two distinct amino acid residues, tryptophan and serine, within porous metal-macrocycle framework-1 via precise molecular recognition at multiple binding sites on the pore surface. Single-crystal X-ray diffraction analysis showed that the indole ring of an N-protected tryptophan molecule was effectively encapsulated within a binding pocket located at the bottom corners of the nanochannel, forming multipoint hydrogen bonds and CH-π interactions. In addition to tryptophan, N-protected serine was adsorbed onto the ceiling sites via multipoint hydrogen bonds. Moreover, modifying their protecting groups allowed us to control the relative positions of the two residues in the nanochannel. We further tested the co-adsorption of both residues in selective separation experiments. The results suggest that designing porous crystals with multiple binding sites is an effective strategy for precise heteroleptic arrangement of amino acid residues, resulting in enhanced functionalization of porous materials.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"1 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-06-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144192835","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}

引用次数: 0

Spontaneous Conversion of Pyridine N-Oxide Ylide Covalent Organic Framework (COF) into Biradical COF as an Efficient Catalyst in Catalytic Dehydrogenation of Nitrogen Heterocycles 吡啶n -氧化物Ylide共价有机骨架（COF）自发转化为双自由基COF的高效催化剂在氮杂环催化脱氢中的作用

IF 8.4 1区化学

Chemical Science Pub Date : 2025-06-02 DOI: 10.1039/d4sc08236b

Wenying Ai, Jiawei Zou, Zhenfeng Cao, Kun Cui, Jianbing Gu, Lina Du, Xin Peng, Mingli Jiao, Tao Shen, Lingbo Qu

{"title":"Spontaneous Conversion of Pyridine N-Oxide Ylide Covalent Organic Framework (COF) into Biradical COF as an Efficient Catalyst in Catalytic Dehydrogenation of Nitrogen Heterocycles","authors":"Wenying Ai, Jiawei Zou, Zhenfeng Cao, Kun Cui, Jianbing Gu, Lina Du, Xin Peng, Mingli Jiao, Tao Shen, Lingbo Qu","doi":"10.1039/d4sc08236b","DOIUrl":"https://doi.org/10.1039/d4sc08236b","url":null,"abstract":"Over the past decade, covalent organic frameworks (COFs) have garnered significant attention as supporting materials for the immobilization of radical species, showing great promise in applications such as catalysis, energy storage, and dynamic nuclear polarization. While considerable progress has been made in developing monoradical COFs, the creation of biradically embedded COFs remains a substantial challenge. In this study, we present a novel pyridine N-oxide ylide COF, featuring an electron-withdrawing dicarboxamide group designed to facilitate the formation of a biradical COF (pyridine N-oxide biradical COF). This biradical generation occurs through a spontaneous intramolecular single-electron transfer process under ambient conditions. By integrating both electron-withdrawing and -conjugated units into the pyridine ring, we enhance the stability and formation of biradical species. Our electron paramagnetic resonance (EPR) spectra demonstrate that the COF structure is pivotal in stabilizing and promoting biradical species formation. Further spectroscopic analyses, including FT-IR, XPS, EPR, and 13C CP/MAS NMR, confirm the coexistence of ylides and biradical species within the COF material. Additionally, the COF exhibited promising catalytic activity, serving as an efficient catalyst in the dehydrogenation of nitrogen heterocycles. This work bridges the gap between ylide COFs and biradical COFs, expanding our understanding of porous materials and their potential applications in advanced chemistry.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"4 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-06-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144192884","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}

引用次数: 0

High-resolution structure of Zn3(HOTP)2 (HOTP = hexaoxidotri-phenylene), a three-dimensional conductive MOF 三维导电MOF Zn3(HOTP)2 （HOTP =六氧化三苯基）的高分辨率结构

IF 8.4 1区化学

Chemical Science Pub Date : 2025-06-02 DOI: 10.1039/d5sc00894h

Kimberly Jane Zhang, Tianyang Chen, Julius Oppenheim, Luming Yang, Lukáš Palatinus, Peter Müller, Troy Van Voorhis, Mircea Dincă

{"title":"High-resolution structure of Zn3(HOTP)2 (HOTP = hexaoxidotri-phenylene), a three-dimensional conductive MOF","authors":"Kimberly Jane Zhang, Tianyang Chen, Julius Oppenheim, Luming Yang, Lukáš Palatinus, Peter Müller, Troy Van Voorhis, Mircea Dincă","doi":"10.1039/d5sc00894h","DOIUrl":"https://doi.org/10.1039/d5sc00894h","url":null,"abstract":"Although two-dimensional (2D) electrically conducting metal-organic frameworks (cMOFs) have become prominent due to their numerous potential applications, their structures are often implied or assumed from rather crude powder X-ray diffrac-tion data. Indeed, exceedingly few examples exist of atomic-level structural details coming from single crystal diffraction experiments. Most widely studied among cMOFs are materials based on triphenylene ligands, in particular M3(HOTP)2 (M = Ni, Cu, Zn) and [M3(HOTP)2][M3(HOTP)]2 (M = Mg, Co; H6HOTP = 2,3,6,7,10,11-hexahydroxytriphenylene), which are invariably described as 2D van der Waals materials with sheets of ligands connected by square planar or octahedral metal ions. Here, we employ electron diffraction to show that, unlike the Mg, Co, Ni, and Cu analogs, Zn3(HOTP)2 crystallizes into a three-dimensional network that is analogous to the structures of the lanthanide-based HOTP MOFs. Moreover, similar to the lanthanide frameworks, Zn3(HOTP)2 exhibits incommensurate modulation, likely originating from a frustration between the preferred π-π stacking distance and the Zn-O bond lengths, or from a Peierls distortion. This work reinforces the importance of employing single crystal diffraction measurements for the characterization of conductive MOFs, especially when trying to correlate electronic properties to structural details.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"81 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-06-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144201758","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}

引用次数: 0