Chemical Science最新文献_第5页

Zirconium-Mediated Carbon-Fluorine Bond Functionalisation Through Cyclohexyne “Umpolung” 锆介导的环己烷“Umpolung”碳氟键功能化

IF 8.4 1区化学

Chemical Science Pub Date : 2025-01-16 DOI: 10.1039/d4sc08522a

Sara Bonfante, Theo Tanner, Christian Lorber, Jason Martin Lynam, Antoine Simonneau, John M. Slattery

引用次数: 0

Introducing halogen-bonded gates in zeolitic frameworks for efficient benzene/cyclohexene/cyclohexane separation 在沸石骨架中引入卤素键合栅极，用于苯/环己烯/环己烷的高效分离

IF 8.4 1区化学

Chemical Science Pub Date : 2025-01-15 DOI: 10.1039/d4sc06624c

Zi-Jun Liang, Fang-Di Dong, Le Ye, Kai Zheng, Ding-Yi Hu, Xi Feng, Wen-Yu Su, Zhi-Shuo Wang, Mu-Yang Zhou, Zi-Luo Fang, Dong-Dong Zhou, Jie-Peng Zhang, Xiao-Ming Chen

引用次数: 0

Different p-Block Elements Induce C3[111] Octahedral Distortion on Titanium to Generate Intense Nonlinear Effect 不同p块元素诱导钛表面C3[111]八面体畸变产生强烈的非线性效应

IF 8.4 1区化学

Chemical Science Pub Date : 2025-01-15 DOI: 10.1039/d4sc06620k

Zhenhua Li, Zhengli Liang, Jiahao Wan, Lehui Liu, Chunxiang Wu, Ping Wang, Xing-Xing Jiang, Zheshuai Lin, Hongming Liu

{"title":"Different p-Block Elements Induce C3[111] Octahedral Distortion on Titanium to Generate Intense Nonlinear Effect","authors":"Zhenhua Li, Zhengli Liang, Jiahao Wan, Lehui Liu, Chunxiang Wu, Ping Wang, Xing-Xing Jiang, Zheshuai Lin, Hongming Liu","doi":"10.1039/d4sc06620k","DOIUrl":"https://doi.org/10.1039/d4sc06620k","url":null,"abstract":"Acentric crystalline materials are the cornerstone of numerous cutting-edge technologies and have been highly sought-after, but they are difficult to construct controllably. Herein, by introducing a new p-block element to break the symmetrical environment of the d0 transition metal in the centric matrix TiTe3O8, a novel acentric tellurite sulfate, namely Ti(TeO3)(SO4), was successfully constructed. In its structure, two types of p-block element-centered oxo-anionic groups, i.e. [TeO3] and [SO4], induce [TiO6] an out-of-center distortion along the local C3[111] direction, which is rare in titanium oxides containing lone-pair cation. The synergy of distorted [TiO6] octahedron, lone-pair [TeO3] pyramid and rigid [SO4] tetrahedron within its structure induces a strong second harmonic generation (SHG) response of 11.6×KDP (KH2PO4), the largest value among mercury-free sulfates. Additionally, Ti(TeO3)(SO4) also shows the largest birefringence (0.145) among sulfates possessing SHG response of more than ten times of KDP, showing huge potential as a nonlinear optical material. The successful implementation of the strategy of inducing intra-octahedral distortion in d0 transition metal by different p-block elements provides new opportunities for constructing acentric structures and exploiting outstanding nonlinear optically active sulfates.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"4 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142981318","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

Grappa – a machine learned molecular mechanics force field Grappa -一个机器学习分子力学力场

IF 8.4 1区化学

Chemical Science Pub Date : 2025-01-15 DOI: 10.1039/d4sc05465b

Leif Seute, Eric Hartmann, Jan Stühmer, Frauke Gräter

{"title":"Grappa – a machine learned molecular mechanics force field","authors":"Leif Seute, Eric Hartmann, Jan Stühmer, Frauke Gräter","doi":"10.1039/d4sc05465b","DOIUrl":"https://doi.org/10.1039/d4sc05465b","url":null,"abstract":"Simulating large molecular systems over long timescales requires force fields that are both accurate and efficient. In recent years, E(3) equivariant neural networks have lifted the tension between computational efficiency and accuracy of force fields, but they are still several orders of magnitude more expensive than established molecular mechanics (MM) force fields. Here, we propose Grappa, a machine learning framework to predict MM parameters from the molecular graph, employing a graph attentional neural network and a transformer with symmetry-preserving positional encoding. The resulting Grappa force field outperforms tabulated and machine-learned MM force fields in terms of accuracy at the same computational efficiency and can be used in existing Molecular Dynamics (MD) engines like GROMACS and OpenMM. It predicts energies and forces of small molecules, peptides, and RNA at state-of-the-art MM accuracy, while also reproducing experimentally measured values for J-couplings. With its simple input features and high data-efficiency, Grappa is well suited for extensions to uncharted regions of chemical space, which we show on the example of peptide radicals. We demonstrate Grappa's transferability to macromolecules in MD simulations from a small fast-folding protein up to a whole virus particle. Our force field sets the stage for biomolecular simulations closer to chemical accuracy, but with the same computational cost as established protein force fields.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"17 4 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142981315","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

Periodic Law-Guided Design of Highly Stable O3-Type Layered Oxide Cathodes for Practical Sodium-Ion Batteries 实用钠离子电池高稳定o3型层状氧化物阴极的周期律指导设计

IF 8.4 1区化学

Chemical Science Pub Date : 2025-01-15 DOI: 10.1039/d4sc08351b

Yuan-Bo Wu, Hai-Yan Hu, Jia-Yang Li, Hanghang Dong, Yan-Fang Zhu, Shuangqiang Chen, Nana Wang, Jiazhao Wang, Yao Xiao

{"title":"Periodic Law-Guided Design of Highly Stable O3-Type Layered Oxide Cathodes for Practical Sodium-Ion Batteries","authors":"Yuan-Bo Wu, Hai-Yan Hu, Jia-Yang Li, Hanghang Dong, Yan-Fang Zhu, Shuangqiang Chen, Nana Wang, Jiazhao Wang, Yao Xiao","doi":"10.1039/d4sc08351b","DOIUrl":"https://doi.org/10.1039/d4sc08351b","url":null,"abstract":"O3-type NaNi0.5Mn0.5O2 cathode material exhibits significant potential for sodium-ion batteries (SIBs) owing to its high theoretical capacity and ample sodium reservoir. Nonetheless, its practical implementation encounters considerable obstacles, such as impaired structural integrity, sensitivity to moisture, inadequate high temperature stability, and unstable at high voltage conditions. This study investigates the co-substitution of Cu, Mg, and Ti, guided by principles of the periodic law, to enhance the material’s stability under varying conditions. The substituent elements were selected based on their atomic properties and introduced into specific sites within the structure: Cu and Mg were substituted at Ni sites, while Ti replaced Mn sites. These modifications strengthened the crystal lattice, mitigating phase transitions, and improved electrochemical performance. The O3- NaNi0.4Cu0.05Mg0.05Mn0.3Ti0.2O2 material exhibited remarkable moisture stability, maintaining 85% of its capacity after 1000 cycles at 5C in 2.0–4.0 V. It also exhibited reversible phase transitions at voltages up to 4.3 V, with no oxygen release observed even when charged to 4.5 V. Furthermore, it exhibited remarkable high-temperature stability in half-cell testing and excellent cycle performance in full-cell evaluations. These results are very helpful for designing high-performance SIB cathodes that can withstand a variety of operating circumstances and ensuring structural stability.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"89 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142981316","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

Photodegradation reveals that singlet energy transfer impedes energy-gradient-driven singlet ﬁssion in polyacene blends 光降解揭示出单线能量转移阻碍了聚乙炔共混物中由能量梯度驱动的单线能量消耗

IF 8.4 1区化学

Chemical Science Pub Date : 2025-01-14 DOI: 10.1039/d4sc06702a

Alexandra N. Stuart, Jessica de la Perrelle, David Mark Huang, Tak W. Kee

{"title":"Photodegradation reveals that singlet energy transfer impedes energy-gradient-driven singlet ﬁssion in polyacene blends","authors":"Alexandra N. Stuart, Jessica de la Perrelle, David Mark Huang, Tak W. Kee","doi":"10.1039/d4sc06702a","DOIUrl":"https://doi.org/10.1039/d4sc06702a","url":null,"abstract":"Singlet fission (SF) is a process that is potentially beneficial for photovoltaics by producing two triplet excitons from a single photon, but its application is often hindered by the inability to effectively separate the resultant triplet excitons. It has been proposed that an energy gradient can assist in separating triplet excitons through triplet energy transfer between chromophores of different triplet energies, but this approach has only been studied in solution and the efficacy of this strategy in the solid state is under explored. Here, we investigate energy-gradient-driven SF in a disordered solid state, in the form of suspensions of 5,12-bis(triisopropylsilylethnyl)tetracene:6,13-bis(triisopropylsilylethnyl)pentance (TIPS-Tn:TIPS-Pn) blend nanoparticles (NPs). Rather than using more conventional techniques such as ultrafast (sub-nanosecond) spectroscopy, we study the photophysics in these NPs through monitoring their photodegradation. TIPS-Tn photodegrades rapidly in neat NPs, but this photodegradation is suppressed upon the addition of TIPS-Pn, indicating a decrease in the TIPS-Tn triplet population. By modeling the photodegradation over a timescale of minutes to hours, we are able to reveal details of processes on the ultrafast timescale. We show that triplet energy transfer occurs from TIPS-Tn to TIPS-Pn, leading to slower photodegradation for TIPS-Tn, and faster photodegradation for TIPS-Pn. However, modeling additionally indicates that singlet energy transfer from TIPS-Tn to TIPS-Pn also occurs, and in fact acts to reduce the efficiency of TIPS-Tn SF. Hence, in this particular system, the energy gradient impedes SF, rather than assisting it. These findings indicate that chromophore pairs must be carefully selected to switch off singlet energy transfer for the energy-gradient approach to be effective in enhancing SF.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"14 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142975509","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

Unravelling the pH-depended mechanism of ferroelectric polarization on different dynamic pathways of photoelectrochemical water oxidation 揭示铁电极化在光电化学水氧化的不同动态路径上的 pH 值依赖机制

IF 8.4 1区化学

Chemical Science Pub Date : 2025-01-14 DOI: 10.1039/d4sc08291e

Xing Ji, Zhouhao Zhu, Ming Zhou, Ying Zhang, Li-Yong Gan, Yunhuai Zhang, Peng Xiao

{"title":"Unravelling the pH-depended mechanism of ferroelectric polarization on different dynamic pathways of photoelectrochemical water oxidation","authors":"Xing Ji, Zhouhao Zhu, Ming Zhou, Ying Zhang, Li-Yong Gan, Yunhuai Zhang, Peng Xiao","doi":"10.1039/d4sc08291e","DOIUrl":"https://doi.org/10.1039/d4sc08291e","url":null,"abstract":"Ferroelectric polarization is considered to be an effective strategy capable of improving the oxygen evolution reaction (OER) of photoelectrocatalysis. The frontier challenge is to clarify how the polarization field control the OER dynamic pathway from molecular details. Here, using the electrochemical fingerprints tests together with theoretical calculations, we systematically investigate the free energy change of oxo and hydroxyl intermediates on TiO2-BaTiO3 core-shell nanowires (BTO@TiO₂) under polarization in different pH environments. We demonstrate that in the adsorbate evolution mechanism (AEM) dominated in acid environment, both positive and negative polarization result in a reduction of the oxo free energy, thereby inhibiting the reaction kinetics. In the oxide path mechanism (OPM) occurred mainly in alkaline condition, ferroelectric polarization exhibits a repulsive adsorbate-adsorbate interactions for OH- coverage and free energy shift of hydroxyl groups. We elucidate that a weakly alkaline electrolyte is the optimal application environment for ferroelectric polarization, the positive polarization promotes the OH- coverage and facilitate reaction pathway transfer from AEM to OPM, thus BTO@TiO2 exhibited a record polarization enhancement of 0.52 mA/cm2 at 1.23 VRHE in pH=11. This work provides a more accurate insights into the pH-depended effect of ferroelectric polarization on OER dynamic pathway than conventional models that are based solely on the band bending regulation.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"1 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142975508","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

Stepwise reduction of an asymmetric π-expanded pyracylene towards the crystalline radical trianion. 不对称π膨胀吡炔逐步还原为结晶自由基三阴离子。

IF 7.6 1区化学

Chemical Science Pub Date : 2025-01-13 DOI: 10.1039/d4sc08255a

Yikun Zhu, Jan Borstelmann, Christian Neiss, Zheng Wei, Andreas Görling, Milan Kivala, Marina A Petrukhina

{"title":"Stepwise reduction of an asymmetric π-expanded pyracylene towards the crystalline radical trianion.","authors":"Yikun Zhu, Jan Borstelmann, Christian Neiss, Zheng Wei, Andreas Görling, Milan Kivala, Marina A Petrukhina","doi":"10.1039/d4sc08255a","DOIUrl":"https://doi.org/10.1039/d4sc08255a","url":null,"abstract":"The chemical reduction of a pyracylene-hexa-peri-hexabenzocoronene-(HBC)-fused nanographene TPP was investigated with K and Rb metals to reveal its multi-electron acceptor abilities. The in situ reaction of TPP with the above alkali metals, monitored by UV-vis-NIR and 1H NMR spectroscopy, evidenced the stepwise reduction process. The use of different solvents and secondary ligands enabled isolation of single crystals of three different reduced states of TPP with 1, 2, and 3 electrons added to its π-system. This provided a unique set of carbanions with gradually increasing negative charge for in-depth structural analysis of the outcomes of controlled electron addition to a non-planar and asymmetric nanographene, using X-ray crystallographic, spectroscopic, and theoretical tools. EPR spectroscopy measurements of the mono- and triply-reduced TPP products revealed distinct EPR splitting patterns. DFT calculations demonstrated a notable difference in the spin density distribution of these two open-shell products and provided insights into experimental EPR data. Moreover, the influence of the counterions on the \"naked\" TPP anions was illustrated computationally.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":7.6,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11744371/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143000712","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

Radical trifluoromethoxylation of fluorinated alkenes for accessing difluoro(trifluoromethoxy)methyl groups 为获得二氟（三氟甲氧基）甲基而进行的氟化烯烃自由基三氟甲氧基化

IF 8.4 1区化学

Chemical Science Pub Date : 2025-01-13 DOI: 10.1039/d4sc07788a

Koki Kawai, Mai Usui, Sota Ikawa, Naoyuki Hoshiya, Yosuke Kishikawa, Norio Shibata

引用次数: 0

Competing pathways to aromaticity governed by amine dehydrogenation and metal-organic complexation in on-surface synthesis. 在表面合成中由胺脱氢和金属-有机络合控制的芳香性竞争途径。

IF 7.6 1区化学

Chemical Science Pub Date : 2025-01-13 DOI: 10.1039/d4sc07550a

Andrés Lombana, Songpol Chaunchaiyakul, Olivier Chuzel, Denis Hagebaum-Reignier, Jean-Luc Parrain, Franck Bocquet, Laurent Nony, Christian Loppacher, Federica Bondino, Elena Magnano, Hiroshi Imada, Emiko Kazuma, Yousoo Kim, Luca Giovanelli, Sylvain Clair

{"title":"Competing pathways to aromaticity governed by amine dehydrogenation and metal-organic complexation in on-surface synthesis.","authors":"Andrés Lombana, Songpol Chaunchaiyakul, Olivier Chuzel, Denis Hagebaum-Reignier, Jean-Luc Parrain, Franck Bocquet, Laurent Nony, Christian Loppacher, Federica Bondino, Elena Magnano, Hiroshi Imada, Emiko Kazuma, Yousoo Kim, Luca Giovanelli, Sylvain Clair","doi":"10.1039/d4sc07550a","DOIUrl":"https://doi.org/10.1039/d4sc07550a","url":null,"abstract":"We investigated the reactivity of a gem-dichlorovinyl-carbazole precursor in the on-surface synthesis approach. Our findings reveal that, on the Au(111) surface, the thermally-induced dehalogenation reaction led to the formation of cumulene dimers. Contrastingly, the more reactive Cu(111) surface promoted the formation of a polyheterocyclic compound exhibiting extended aromaticity. The latter was found to be related to the dehydrogenation of the amine groups, which did not occur on Au(111), thus promoting the different reactivity observed. At higher annealing temperature, selective C-H activation led to the formation of well-defined organometallic chains. In addition, we found that the amine complexation with metal adatom on Cu(111) was an inhibiting factor for the dimerization reaction, a challenge that could be overcome through proper control of the deposition conditions.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":7.6,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11744327/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143001041","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