Chem最新文献_第9页

Stable and responsive atropisomerism around a carbon–iodine bond 碳-碘键周围稳定且反应迅速的反旋异构

IF 23.5 1区化学

Chem Pub Date : 2025-04-04 DOI: 10.1016/j.chempr.2025.102527

Shohei Abe, Jun Kikuchi, Arimasa Matsumoto, Naohiko Yoshikai

引用次数: 0

A programmable modular robot for the synthesis of molecular machines 用于合成分子机器的可编程模块化机器人

IF 23.5 1区化学

Chem Pub Date : 2025-03-31 DOI: 10.1016/j.chempr.2025.102504

Robert Rauschen, Jean-François Ayme, Bartosz M. Matysiak, Dean Thomas, Leroy Cronin

{"title":"A programmable modular robot for the synthesis of molecular machines","authors":"Robert Rauschen, Jean-François Ayme, Bartosz M. Matysiak, Dean Thomas, Leroy Cronin","doi":"10.1016/j.chempr.2025.102504","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102504","url":null,"abstract":"The assembly of molecular nanomachines using atomically precise manipulations promises to enable nanotechnology with unprecedented architectural features and exquisite functional properties. However, this future is critically limited by the ability to autonomously manufacture nanomachines, with current efforts being heavily labor intensive. A system is needed to program and assemble matter under digital control, unifying molecular nanotechnology and macroscale chemical processes. Herein, we present a universal chemical robotic synthesis platform (Chemputer) that produces functional molecular machines. By integrating autonomous feedback through on-line NMR and liquid chromatography, a divergent four-step synthesis and purification of molecular rotaxane architectures are achieved. The synthetic sequence averaged 800 base steps over 60 h, affording products on an analytical scale for feasibility studies. While standardizing rotaxane synthesis enhances reliability and reproducibility, our workflow addresses two bottlenecks in autonomous synthesis: yield determination (via on-line <sup>1</sup>H NMR) and product purification via multiple column chromatography techniques (silica gel and size exclusion).","PeriodicalId":268,"journal":{"name":"Chem","volume":"15 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143737282","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

Chlorine-free synthesis of axially chiral organophosphorus compounds from white phosphorus 以白磷为原料无氯合成轴手性有机磷化合物

IF 23.5 1区化学

Chem Pub Date : 2025-03-27 DOI: 10.1016/j.chempr.2025.102496

Xinlei Huangfu, Wei Liu, Zhiyi Song, Junnian Wei, Wen-Xiong Zhang

引用次数: 0

Conventional versus singlet-triplet Kondo effect in Blatter radical molecular junctions: Zero-bias anomalies and magnetoresistance 布拉特自由基分子结中的常规与单重态-三重态近藤效应：零偏置异常和磁电阻

IF 23.5 1区化学

Chem Pub Date : 2025-03-27 DOI: 10.1016/j.chempr.2025.102500

Gautam Mitra, Jueting Zheng, Karen Schaefer, Michael Deffner, Jonathan Z. Low, Luis M. Campos, Carmen Herrmann, Theo A. Costi, Elke Scheer

{"title":"Conventional versus singlet-triplet Kondo effect in Blatter radical molecular junctions: Zero-bias anomalies and magnetoresistance","authors":"Gautam Mitra, Jueting Zheng, Karen Schaefer, Michael Deffner, Jonathan Z. Low, Luis M. Campos, Carmen Herrmann, Theo A. Costi, Elke Scheer","doi":"10.1016/j.chempr.2025.102500","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102500","url":null,"abstract":"The Blatter radical has been suggested as a building block in future molecular spintronic devices because of its radical character and expected long spin lifetime. However, whether its radical character is maintained in single-molecule junctions depends on the environment. Here, we demonstrate the ability to retain the open-shell nature of the Blatter radical in a two-terminal device by the appearance of a Kondo resonance in transport spectroscopy. Additionally, a high negative magnetoresistance is observed in junctions that do not reveal a zero-bias anomaly. By combining distance-dependent and magnetic-field-dependent measurements and accompanying quantum-chemical and quantum-transport calculations, we show that both findings, the negative magnetoresistance and the Kondo features, can be consistently explained by a singlet-triplet Kondo model. Our findings provide the possibility of using the Blatter radical in a two-terminal system under cryogenic conditions and also reveal the magnetotransport properties emerging from different configurations of the molecule inside a junction.","PeriodicalId":268,"journal":{"name":"Chem","volume":"183 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713534","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

Precisely constructing asymmetric triple atoms for highly efficient electrocatalysis 精确构造不对称三原子，用于高效电催化

IF 23.5 1区化学

Chem Pub Date : 2025-03-26 DOI: 10.1016/j.chempr.2025.102498

Jingyan Zhang, Zhongxin Song, Xiaozhang Yao, Yi Guan, Ziwei Huo, Ning Chen, Lei Zhang, Xueliang Sun

引用次数: 0

Directional self-assembly of organic semi-type core-shell microwires for programmable visible-to-near-infrared waveguiding conversion 用于可编程可见光到近红外波导转换的有机半型核壳微线的定向自组装

IF 23.5 1区化学

Chem Pub Date : 2025-03-24 DOI: 10.1016/j.chempr.2025.102497

Bin Wu, Ming-Peng Zhuo, Ying-Li Shi, Lin-Feng Gu, Yu-Dong Zhao, Yang Su, Yuan-Yuan Li, Hang Lu, Wei-Feng Li, Zuo-Shan Wang, Xue-Dong Wang

{"title":"Directional self-assembly of organic semi-type core-shell microwires for programmable visible-to-near-infrared waveguiding conversion","authors":"Bin Wu, Ming-Peng Zhuo, Ying-Li Shi, Lin-Feng Gu, Yu-Dong Zhao, Yang Su, Yuan-Yuan Li, Hang Lu, Wei-Feng Li, Zuo-Shan Wang, Xue-Dong Wang","doi":"10.1016/j.chempr.2025.102497","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102497","url":null,"abstract":"Organic topological structures integrating multi-color emission and waveguide for optical interconnects are of considerable significance in both scientific research and optoelectronic applications. However, limited success in organic near-infrared (NIR) emitters and difficult manipulation of intermolecular interactions lead to a severe restriction of the photon waveguide for optical communication. Herein, we have purposefully designed dibenzothiophene-based charge-transfer (CT) cocrystals with tunable NIR emission from 710 to 840 nm via finely increasing their aggregation closeness and CT interaction intensity. The controlled molecular stacking evolution from a loosely to a tightly mixed stack achieved a desired narrowed optical band gap of 1.8 eV. Furthermore, these CT cocrystals with a low optical loss coefficient of 0.077 dB/μm at 840 nm were introduced into NIR-emissive semi-type core-shell heterostructures, which realized effective energy transfer with a high conversion efficiency of 40.5% between visible and NIR emission. This strategy paves the way toward precise processing of photons with transmission wavelengths for integrated optoelectronics.","PeriodicalId":268,"journal":{"name":"Chem","volume":"59 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143677964","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

Electrochemical 6Li isotope enrichment based on selective insertion in 1D tunnel-structured V2O5 基于一维隧道结构V2O5中选择性插入的电化学6Li同位素富集

IF 23.5 1区化学

Chem Pub Date : 2025-03-20 DOI: 10.1016/j.chempr.2025.102486

J. Luis Carrillo, Andrew A. Ezazi, Saul Perez-Beltran, Carlos A. Larriuz, Harris Kohl, Jaime A. Ayala, Arnab Maji, Stanislav Verkhoturov, Mohammed Al-Hashimi, Hassan Bazzi, Conan Weiland, Cherno Jaye, Daniel A. Fischer, Lucia Zuin, Jian Wang, Sarbajit Banerjee

{"title":"Electrochemical 6Li isotope enrichment based on selective insertion in 1D tunnel-structured V2O5","authors":"J. Luis Carrillo, Andrew A. Ezazi, Saul Perez-Beltran, Carlos A. Larriuz, Harris Kohl, Jaime A. Ayala, Arnab Maji, Stanislav Verkhoturov, Mohammed Al-Hashimi, Hassan Bazzi, Conan Weiland, Cherno Jaye, Daniel A. Fischer, Lucia Zuin, Jian Wang, Sarbajit Banerjee","doi":"10.1016/j.chempr.2025.102486","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102486","url":null,"abstract":"The renaissance of nuclear energy has generated substantial demand for <sup>6</sup>Li as a target for nuclear bombardment reactions to produce tritium fuel in breeder reactors. Conventional isotope separation methods utilize differential solubility in mercury amalgams, which pose performance, toxicity, and sustainability concerns. Here, we show that hybrid capacitive deionization wherein Li ions are inserted from aqueous media within the 1D tunnels of a metastable polymorph, ζ-V<sub>2</sub>O<sub>5</sub>, can be used to selectively sequester <sup>6</sup>Li ions. An enrichment factor of ca. 57‰ is achieved. X-ray scattering, spectroscopy, and operando spectromicroscopy studies indicate that Li ions are sequestered within 1D tunnels of ζ-V<sub>2</sub>O<sub>5</sub> through faradaic processes. <sup>6</sup>Li and <sup>7</sup>Li ions are found to migrate at different rates because of subtly different coordination environments. The results illustrate that ζ-V<sub>2</sub>O<sub>5</sub> can be utilized as a discriminating host to selectively sequester and enrich <sup>6</sup>Li from natural abundance precursor flow streams and suggest a distinctive mode of achieving viable isotope separation.","PeriodicalId":268,"journal":{"name":"Chem","volume":"61 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143660511","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

Strong uranium-phosphorus antiferromagnetic exchange coupling in a crystalline diphosphorus radical trianion actinide complex 结晶二磷基三阴离子锕系元素络合物中的强铀磷反铁磁交换耦合

IF 19.1 1区化学

Chem Pub Date : 2025-03-13 DOI: 10.1016/j.chempr.2024.10.004

Jingzhen Du , Benjamin E. Atkinson , John A. Seed , Rebecca F. Sheppard , Floriana Tuna , Ashley J. Wooles , Nicholas F. Chilton , Stephen T. Liddle

{"title":"Strong uranium-phosphorus antiferromagnetic exchange coupling in a crystalline diphosphorus radical trianion actinide complex","authors":"Jingzhen Du , Benjamin E. Atkinson , John A. Seed , Rebecca F. Sheppard , Floriana Tuna , Ashley J. Wooles , Nicholas F. Chilton , Stephen T. Liddle","doi":"10.1016/j.chempr.2024.10.004","DOIUrl":"10.1016/j.chempr.2024.10.004","url":null,"abstract":"<div><div>The dominant form of elemental nitrogen on Earth is dinitrogen, but elemental phosphorus is found predominantly as white phosphorus or other singly bonded allotropes. Thus, there is interest in studying diphosphorus derivatives, most notably trapping between metal ions affording diphosphorus in +2, +1⋅, 0, 1−⋅, 2−, and 4− charge states. However, the diphosphorus radical trianion form had previously remained elusive due to the instability of main-group diatomics with large, odd negative charges. Here, we disclose a crystalline diuranium diphosphorus radical trianion complex with strong antiferromagnetic uranium-phosphorus magnetic exchange coupling parameters of up to −731 cm<sup>−1</sup>. This value is over five times greater than that of lanthanide analogues and is comparable to or exceeds d-block metal-metal and metal-ligand exchange couplings, despite being based on a 5f metal, which is typically regarded as possessing contracted valence orbitals compared with d-block ions. This highlights exchange-coupled f-element-p-block radical bridged character that can be engendered in molecular magnetism.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 3","pages":"Article 102337"},"PeriodicalIF":19.1,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142562033","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

Boosting narrow-band near-infrared-emitting efficiency of thulium by lattice modulation for reflective absorption bioimaging 通过晶格调制提高铥的窄带近红外发射效率，实现反射吸收生物成像

IF 19.1 1区化学

Chem Pub Date : 2025-03-13 DOI: 10.1016/j.chempr.2024.09.024

Kaina Wang , Jipeng Fu , Sibo Zhan , Hongliang Dong , Chenjie Lou , Tianyi Sun , Jinru Liu , Bingyu Huang , Long Tian , Lihong Jiang , Ran Pang , Su Zhang , Huajie Luo , Mathieu Allix , Xiaojun Kuang , Shiqing Xu , Hongjie Zhang , Mingxue Tang

{"title":"Boosting narrow-band near-infrared-emitting efficiency of thulium by lattice modulation for reflective absorption bioimaging","authors":"Kaina Wang , Jipeng Fu , Sibo Zhan , Hongliang Dong , Chenjie Lou , Tianyi Sun , Jinru Liu , Bingyu Huang , Long Tian , Lihong Jiang , Ran Pang , Su Zhang , Huajie Luo , Mathieu Allix , Xiaojun Kuang , Shiqing Xu , Hongjie Zhang , Mingxue Tang","doi":"10.1016/j.chempr.2024.09.024","DOIUrl":"10.1016/j.chempr.2024.09.024","url":null,"abstract":"<div><div>Near-infrared (NIR) luminescence materials with narrow-band emissions are essential for brain and muscle activity imaging based on the absorption difference of oxygenated proteins. However, most known NIR-emitting materials are limited by low external quantum efficiency (EQE) and broadband properties. This work presents the careful design of Tm, Na-doped strontium sulfide (SrS: Tm<sup>3+</sup>, Na<sup>+</sup>) phosphor for NIR light-emitting diode (LED), which shows a narrow emitting band of 27 nm. The successful incorporation of Na<sup>+</sup> into SrS: Tm<sup>3+</sup> contributes to the suppression of lattice phonons, resulting in significant improvement in EQE from 33.6% to 53.7% and an increase in thermal stability. The efficient host absorption and energy transfer are facilitated by the crystallographic Sr defects and the distortion in the symmetric crystal, disclosed by solid-state NMR, electron paramagnetic resonance (EPR), transient spectra, and X-ray total scattering analysis. Subsequently, efficient identification of vascular patterns based on the differential absorption of hemoglobin enables the potential application of rare-earth luminescent materials in NIR phosphor-converted light-emitting diodes (pc-LEDs) and bioimaging.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 3","pages":"Article 102325"},"PeriodicalIF":19.1,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142452045","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

Remote optical chirality transfer via helical polyaromatic capsules upon encapsulation 通过螺旋多芳香族胶囊封装实现远程光学手性转移

IF 19.1 1区化学

Chem Pub Date : 2025-03-13 DOI: 10.1016/j.chempr.2024.09.031

Hayate Sasafuchi , Mayuko Ueda , Natsuki Kishida , Tomohisa Sawada , Seika Suzuki , Yoshitane Imai , Michito Yoshizawa

{"title":"Remote optical chirality transfer via helical polyaromatic capsules upon encapsulation","authors":"Hayate Sasafuchi , Mayuko Ueda , Natsuki Kishida , Tomohisa Sawada , Seika Suzuki , Yoshitane Imai , Michito Yoshizawa","doi":"10.1016/j.chempr.2024.09.031","DOIUrl":"10.1016/j.chempr.2024.09.031","url":null,"abstract":"<div><div>Helical molecular assemblies have been widely created so far, taking inspiration from helical bioconstructs (e.g., DNAs and proteins). However, the host utilities of such synthetic helices remain largely underdeveloped, particularly as chiroptical nanotools. Here, we report the preparation of new polyaromatic capsules with right- or left-handed quadruple helicity, regulated by chiral saccharide-based side chains attached at the outer surface. The capsule quantitatively encapsulates achiral fluorescent dyes in the cavity. The resultant host-guest complexes display excellent circularly polarized luminescence properties (up to |<em>g</em><sub>lum</sub>| = 1.6 × 10<sup>−2</sup>) derived from the bound dyes, through efficient optical chirality transfer from the outer biochiral groups to the inner achiral dyes via the quadruple helical shell, which represents an unprecedented chiroptical strategy. This nanotool can be applied to spherical fullerene to induce its chirality with high efficiency in solution (up to |<em>g</em><sub>abs</sub>| = 1.0 × 10<sup>−2</sup>) and in the solid state.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 3","pages":"Article 102332"},"PeriodicalIF":19.1,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142536376","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