JACS Au最新文献

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Regio- and Enantioselective Hydromethylation of 3-Pyrrolines and Glycals Enabled by Cobalt Catalysis 钴催化 3-吡咯啉和糖醛的区域和对映体选择性氢甲基化反应
IF 8.5
JACS Au Pub Date : 2024-06-11 DOI: 10.1021/jacsau.4c00275
Mengyang Shen, Caoyue Niu, Xuchao Wang*, Jia-Bo Huang, Zhen Zhao, Shao-Fei Ni* and Zi-Qiang Rong*, 
{"title":"Regio- and Enantioselective Hydromethylation of 3-Pyrrolines and Glycals Enabled by Cobalt Catalysis","authors":"Mengyang Shen,&nbsp;Caoyue Niu,&nbsp;Xuchao Wang*,&nbsp;Jia-Bo Huang,&nbsp;Zhen Zhao,&nbsp;Shao-Fei Ni* and Zi-Qiang Rong*,&nbsp;","doi":"10.1021/jacsau.4c00275","DOIUrl":"10.1021/jacsau.4c00275","url":null,"abstract":"<p >Enantioenriched 3-methylpyrrolidine, with its unique chiral nitrogen-containing core skeleton, exists widely in various functional molecules, including natural products, bioactive compounds, and pharmaceuticals. Traditional methods for synthesizing these valuable methyl-substituted heterocycles often involve enzymatic processes or complex procedures with chiral auxiliaries, limiting the substrate scope and efficiency. Efficient catalytic methylation, especially in an enantioselective manner, has been a long-standing challenge in chemical synthesis. Herein, we present a novel approach for the remote and stereoselective installation of a methyl group onto N-heterocycles, leveraging a CoH-catalyzed asymmetric hydromethylation strategy. By effectively combining a commercial cobalt precursor with a modified bisoxazoline (BOX) ligand, a variety of easily accessible 3-pyrrolines can be converted to valuable enantiopure 3-(isotopic labeling)methylpyrrolidine compounds with outstanding enantioselectivity. This efficient protocol streamlines the two-step synthesis of enantioenriched 3-methylpyrrolidine, which previously required up to five or six steps under harsh conditions or expensive starting materials.</p>","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":null,"pages":null},"PeriodicalIF":8.5,"publicationDate":"2024-06-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/jacsau.4c00275","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141357638","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Archimedean Spirals with Controllable Chirality: Disk Substrate-Mediated Solution Assembly of Rod–Coil Block Copolymers 具有可控手性的阿基米德螺旋:圆盘基质介导的杆卷嵌段共聚物溶液组装
IF 8.5
JACS Au Pub Date : 2024-06-11 DOI: 10.1021/jacsau.4c00324
Chunhua Cai, Hongfeng Tang, Feiyan Li, Zhanwen Xu*, Jiaping Lin*, Da Li, Zhengmin Tang, Chunming Yang and Liang Gao, 
{"title":"Archimedean Spirals with Controllable Chirality: Disk Substrate-Mediated Solution Assembly of Rod–Coil Block Copolymers","authors":"Chunhua Cai,&nbsp;Hongfeng Tang,&nbsp;Feiyan Li,&nbsp;Zhanwen Xu*,&nbsp;Jiaping Lin*,&nbsp;Da Li,&nbsp;Zhengmin Tang,&nbsp;Chunming Yang and Liang Gao,&nbsp;","doi":"10.1021/jacsau.4c00324","DOIUrl":"10.1021/jacsau.4c00324","url":null,"abstract":"<p >Spirals are common in nature; however, they are rarely observed in polymer self-assembly systems, and the formation mechanism is not well understood. Herein, we report the formation of two-dimensional (2D) spiral patterns via microdisk substrate-mediated solution self-assembly of polypeptide-based rod–coil block copolymers. The spiral pattern consists of multiple strands assembled from the block copolymers, and two central points are observed. The spirals fit well with the Archimedean spiral model, and their chirality is dependent on the chirality of the polypeptide blocks. As revealed by a combination of experiments and theoretical simulations, these spirals are induced by an interplay of the parallel ordering tendency of the strands and circular confinement of the microdisks. This work presents the first example regarding substrate-mediated self-assembly of block copolymers into spirals. The gained information could not only enhance our understanding of natural spirals but also assist in both the controllable preparations and applications of spiral nanostructures.</p>","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":null,"pages":null},"PeriodicalIF":8.5,"publicationDate":"2024-06-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/jacsau.4c00324","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141356871","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Multiple Interlayer Interactions Enable Highly Stable X-ray Detection in 2D Hybrid Perovskites 多重层间相互作用使二维混合包光体中的 X 射线探测高度稳定
IF 8.5
JACS Au Pub Date : 2024-06-10 DOI: 10.1021/jacsau.4c00345
Haiqing Zhong, Shihai You*, Jianbo Wu, Zeng-Kui Zhu, Panpan Yu, Hang Li, Zi-Yang Wu, Yang Li, Qianwen Guan, Hongliang Dai, Chang Qu, Jiahong Wang, Shuang Chen, Chengmin Ji and Junhua Luo*, 
{"title":"Multiple Interlayer Interactions Enable Highly Stable X-ray Detection in 2D Hybrid Perovskites","authors":"Haiqing Zhong,&nbsp;Shihai You*,&nbsp;Jianbo Wu,&nbsp;Zeng-Kui Zhu,&nbsp;Panpan Yu,&nbsp;Hang Li,&nbsp;Zi-Yang Wu,&nbsp;Yang Li,&nbsp;Qianwen Guan,&nbsp;Hongliang Dai,&nbsp;Chang Qu,&nbsp;Jiahong Wang,&nbsp;Shuang Chen,&nbsp;Chengmin Ji and Junhua Luo*,&nbsp;","doi":"10.1021/jacsau.4c00345","DOIUrl":"10.1021/jacsau.4c00345","url":null,"abstract":"<p >Metal halide perovskites have outperformed conventional inorganic semiconductors in direct X-ray detection due to their ease of synthesis and intriguing photoelectric properties. However, the operational instability caused by severe ion migration under a high external electric field is still a big concern for the practical application of perovskite detectors. Here, we report a 2D (BPEA)<sub>2</sub>PbI<sub>4</sub> (BPEA = <i>R</i>-1-(4-bromophenyl)ethylammonium) perovskite with Br-substituted aromatic spacer capable of introducing abundant interactions, e.g., the molecular electrostatic forces between Br atoms and aromatic rings and halogen bonds of Br–I, in the interlayer space, which effectively suppresses ion migration and thus enables superior operational stability. Constructing direct X-ray detectors based on high-quality single crystals of (BPEA)<sub>2</sub>PbI<sub>4</sub> results in a high sensitivity of 1,003 μC Gy<sup>–1</sup> cm<sup>–2</sup>, a low detection limit of 366 nGy s<sup>–1</sup>, and an ultralow baseline drift of 3.48 × 10<sup>–8</sup> nA cm<sup>–1</sup> s<sup>–1</sup> V<sup>–1</sup> at 80 V bias. More strikingly, it also exhibits exceptional operational stability under high flux, long-time X-ray irradiation, and large working voltage. This work shows an integration of multiple interlayer interactions to stabilize perovskite X-ray detectors, providing new insights into the future design of perovskite optoelectronic devices toward practical application.</p>","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":null,"pages":null},"PeriodicalIF":8.5,"publicationDate":"2024-06-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/jacsau.4c00345","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141361648","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Rational Design of Pyrido[3,2-b]indolizine as a Tunable Fluorescent Scaffold for Fluorogenic Bioimaging 将吡啶并[3,2-b]吲嗪作为可调荧光支架用于荧光生物成像的合理设计
IF 8.5
JACS Au Pub Date : 2024-06-10 DOI: 10.1021/jacsau.4c0013510.1021/jacsau.4c00135
Sihyeong Yi, Dahham Kim, Wansang Cho, Jung Ho Lee, Ji Hoon Kwon, Jonghoon Kim* and Seung Bum Park*, 
{"title":"Rational Design of Pyrido[3,2-b]indolizine as a Tunable Fluorescent Scaffold for Fluorogenic Bioimaging","authors":"Sihyeong Yi,&nbsp;Dahham Kim,&nbsp;Wansang Cho,&nbsp;Jung Ho Lee,&nbsp;Ji Hoon Kwon,&nbsp;Jonghoon Kim* and Seung Bum Park*,&nbsp;","doi":"10.1021/jacsau.4c0013510.1021/jacsau.4c00135","DOIUrl":"https://doi.org/10.1021/jacsau.4c00135https://doi.org/10.1021/jacsau.4c00135","url":null,"abstract":"<p >Novel fluorescent scaffolds are highly demanding for a wide range of applications in biomedical investigation. To meet this demand, the pyrido[3,2-<i>b</i>]indolizine scaffold was designed as a versatile organic fluorophore. With the aid of computational modeling, fluorophores offering tunable emission colors (blue to red) were constructed. Notably, constructed fluorophores absorb lights in the visible range (&gt;400 nm) despite their small sizes (&lt;300 g/mol). Among the fluorophores was discovered a highly fluorogenic fluorophore with a unique turn-on property, <b>1</b>, and it was developed into a washing-free bioprobe for visualizing cellular lipid droplets in living cells. Furthermore, motivated by the core’s compact size and structural analogy to indole, unprecedented tryptophan-analogous fluorogenic unnatural amino acids were constructed and incorporated into fluorogenic peptide probes for monitoring peptide–protein interactions.</p>","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":null,"pages":null},"PeriodicalIF":8.5,"publicationDate":"2024-06-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/jacsau.4c00135","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142075682","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Redox-Responsive Halogen Bonding as a Highly Selective Interaction for Electrochemical Separations 氧化还原反应卤素键作为电化学分离的高选择性相互作用
IF 8.5
JACS Au Pub Date : 2024-06-10 DOI: 10.1021/jacsau.4c0026510.1021/jacsau.4c00265
Nayeong Kim, Vijaya S. Jeyaraj, Johannes Elbert, Sung Jin Seo, Alexander V. Mironenko and Xiao Su*, 
{"title":"Redox-Responsive Halogen Bonding as a Highly Selective Interaction for Electrochemical Separations","authors":"Nayeong Kim,&nbsp;Vijaya S. Jeyaraj,&nbsp;Johannes Elbert,&nbsp;Sung Jin Seo,&nbsp;Alexander V. Mironenko and Xiao Su*,&nbsp;","doi":"10.1021/jacsau.4c0026510.1021/jacsau.4c00265","DOIUrl":"https://doi.org/10.1021/jacsau.4c00265https://doi.org/10.1021/jacsau.4c00265","url":null,"abstract":"<p >Leveraging specific noncovalent interactions can broaden the mechanims for selective electrochemical separations beyond solely electrostatic interactions. Here, we explore redox-responsive halogen bonding (XB) for selective electrosorption in nonaqueous media, by taking advantage of directional interactions of XB alongisde a cooperative and synergistic ferrocene redox-center. We designed and evaluated a new redox-active XB donor polymer, poly(5-iodo-4-ferrocenyl-1-(4-vinylbenzyl)-1<i>H</i>-1,2,3-triazole) (P(FcTS-I)), for the electrochemically switchable binding and release of target organic and inorganic ions at a heterogeneous interface. Under applied potential, the oxidized ferrocene amplifies the halogen binding site, leading to significantly enhanced uptake and selectivity towards key inorganic and organic species, including chloride, bisulfate, and benzenesulfonate, compared to the open-circuit potential or the hydrogen bonding donor analog. Density functional theory calculations, as well as spectroscopic analysis, offer mechanistic insight into the degree of amplification of σ-holes at a molecular level, with selectivity modulated by charge transfer and dispersion interactions. Our work highlights the potential of XB in selective electrosorption by uniquely leveraging noncovalent interactions for redox-mediated electrochemical separations.</p>","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":null,"pages":null},"PeriodicalIF":8.5,"publicationDate":"2024-06-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/jacsau.4c00265","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141959214","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Integrating Au Catalysis and Engineered Amine Dehydrogenase for the Chemoenzymatic Synthesis of Chiral Aliphatic Amines 将金催化与工程胺脱氢酶结合用于手性脂肪胺的化学酶法合成
IF 8.5
JACS Au Pub Date : 2024-06-10 DOI: 10.1021/jacsau.4c00222
Jianqiao Liu, Jing Bai*, Yunting Liu, Liya Zhou, Ying He, Li Ma, Guanhua Liu, Jing Gao and Yanjun Jiang*, 
{"title":"Integrating Au Catalysis and Engineered Amine Dehydrogenase for the Chemoenzymatic Synthesis of Chiral Aliphatic Amines","authors":"Jianqiao Liu,&nbsp;Jing Bai*,&nbsp;Yunting Liu,&nbsp;Liya Zhou,&nbsp;Ying He,&nbsp;Li Ma,&nbsp;Guanhua Liu,&nbsp;Jing Gao and Yanjun Jiang*,&nbsp;","doi":"10.1021/jacsau.4c00222","DOIUrl":"10.1021/jacsau.4c00222","url":null,"abstract":"<p >Direct synthesis of aliphatic amines from alkynes is highly desirable due to its atom economy and high stereoselectivity but still challenging, especially for the long-chain members. Here, a combination of Au-catalyzed alkyne hydration and amine dehydrogenase-catalyzed (AmDH) reductive amination was constructed, enabling sequential conversion of alkynes into chiral amines in aqueous solutions, particularly for the synthesis of long-chain aliphatic amines on a large scale. The production of chiral aliphatic amines with more than 6 carbons reached 36–60 g/L. A suitable biocatalyst [<i>Pt</i>AmDH (A113G/T134G/V294A)], obtained by data mining and active site engineering, enabled the transformation of previously inactive long-chain ketones at high concentrations. Computational analysis revealed that the broader substrate scope and tolerance with the high substrate concentrations resulted from the additive effects of mutations introduced to the three gatekeeper residues 113, 134, and 294.</p>","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":null,"pages":null},"PeriodicalIF":8.5,"publicationDate":"2024-06-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/jacsau.4c00222","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141362529","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Structural, Ionic, and Electronic Properties of Solid-State Phthalimide-Containing Polymers for All-Organic Batteries 用于全有机电池的含邻苯二甲酰亚胺固态聚合物的结构、离子和电子特性
IF 8.5
JACS Au Pub Date : 2024-06-07 DOI: 10.1021/jacsau.4c00276
Riccardo Alessandri, Cheng-Han Li, Sheila Keating, Khirabdhi T. Mohanty, Aaron Peng, Jodie L. Lutkenhaus, Stuart J. Rowan, Daniel P. Tabor* and Juan J. de Pablo*, 
{"title":"Structural, Ionic, and Electronic Properties of Solid-State Phthalimide-Containing Polymers for All-Organic Batteries","authors":"Riccardo Alessandri,&nbsp;Cheng-Han Li,&nbsp;Sheila Keating,&nbsp;Khirabdhi T. Mohanty,&nbsp;Aaron Peng,&nbsp;Jodie L. Lutkenhaus,&nbsp;Stuart J. Rowan,&nbsp;Daniel P. Tabor* and Juan J. de Pablo*,&nbsp;","doi":"10.1021/jacsau.4c00276","DOIUrl":"10.1021/jacsau.4c00276","url":null,"abstract":"<p >Redox-active polymers serving as the active materials in solid-state electrodes offer a promising path toward realizing all-organic batteries. While both cathodic and anodic redox-active polymers are needed, the diversity of the available anodic materials is limited. Here, we predict solid-state structural, ionic, and electronic properties of anodic, phthalimide-containing polymers using a multiscale approach that combines atomistic molecular dynamics, electronic structure calculations, and machine learning surrogate models. Importantly, by combining information from each of these scales, we are able to bridge the gap between bottom-up molecular characteristics and macroscopic properties such as apparent diffusion coefficients of electron transport (<i>D</i><sub>app</sub>). We investigate the impact of different polymer backbones and of two critical factors during battery operation: state of charge and polymer swelling. Our findings reveal that the state of charge significantly influences solid-state packing and the thermophysical properties of the polymers, which, in turn, affect ionic and electronic transport. A combination of molecular-level properties (such as the reorganization energy) and condensed-phase properties (such as effective electron hopping distances) determine the predicted ranking of electron transport capabilities of the polymers. We predict <i>D</i><sub>app</sub> for the phthalimide-based polymers and for a reference nitroxide radical-based polymer, finding a 3 orders of magnitude increase in <i>D</i><sub>app</sub> (≈10<sup>–6</sup> cm<sup>2</sup> s<sup>–1</sup>) with respect to the reference. This study underscores the promise of phthalimide-containing polymers as highly capable redox-active polymers for anodic materials in all-organic batteries, due to their exceptional predicted electron transport capabilities.</p>","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":null,"pages":null},"PeriodicalIF":8.5,"publicationDate":"2024-06-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/jacsau.4c00276","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141371020","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Total Synthesis of the Repeating Units of Highly Functionalized O-Antigens of Pseudomonas aeruginosa ATCC 27577, O10, and O19 铜绿假单胞菌 ATCC 27577、O10 和 O19 的高功能化 O 抗原重复单元的全合成
IF 8.5
JACS Au Pub Date : 2024-06-07 DOI: 10.1021/jacsau.4c00321
Xiaoyu Yang, Han Zhang, Qingpeng Zhao, Qingjiang Li, Tiehai Li and Jian Gao*, 
{"title":"Total Synthesis of the Repeating Units of Highly Functionalized O-Antigens of Pseudomonas aeruginosa ATCC 27577, O10, and O19","authors":"Xiaoyu Yang,&nbsp;Han Zhang,&nbsp;Qingpeng Zhao,&nbsp;Qingjiang Li,&nbsp;Tiehai Li and Jian Gao*,&nbsp;","doi":"10.1021/jacsau.4c00321","DOIUrl":"10.1021/jacsau.4c00321","url":null,"abstract":"<p >The first total synthesis of the repeating units of the <i>O</i>-antigens of <i>Pseudomonas aeruginosa</i> ATCC 27577, O10, and O19 was achieved via a linear glycosylation strategy. This also represents the first synthesis of an oligosaccharide containing an α-linked <i>N</i>-acetyl-<span>l</span>-galactosaminuronic acid (<span>l</span>-Gal<i>p</i>NAcA) unit. All of the glycosyl linkages, including three challenging 1,2-<i>cis</i>-glycosidic bonds of amino sugars, were effectively constructed with high to exclusive stereoselectivity, while orthogonal protection tactics were employed to facilitate regioselective glycosylations and the introduction of a variety of functionalities. An acetyl group migration phenomenon was found during the synthesis of the <i>O</i>-acylated repeating unit of the <i>P. aeruginosa</i> ATCC 27577 antigen. All synthetic targets carried an amino functional group in the linker at the reducing end, thus facilitating further regioselective elaboration and biological studies. The synthetic strategy established here should be useful for the preparation of other similar oligosaccharides.</p>","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":null,"pages":null},"PeriodicalIF":8.5,"publicationDate":"2024-06-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/jacsau.4c00321","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141373130","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Phospholyl and Arsolyl Triple-Decker Sandwich Complexes of Europium(II) and Strontium(II) 铕(II)和锶(II)的膦酰基和胂酰基三癸基三明治配合物
IF 8.5
JACS Au Pub Date : 2024-06-06 DOI: 10.1021/jacsau.4c00300
Noah Schwarz, Julia Feye, Vanitha R. Naina, Ralf Köppe, Sebastian Gillhuber, Xiaofei Sun and Peter W. Roesky*, 
{"title":"Phospholyl and Arsolyl Triple-Decker Sandwich Complexes of Europium(II) and Strontium(II)","authors":"Noah Schwarz,&nbsp;Julia Feye,&nbsp;Vanitha R. Naina,&nbsp;Ralf Köppe,&nbsp;Sebastian Gillhuber,&nbsp;Xiaofei Sun and Peter W. Roesky*,&nbsp;","doi":"10.1021/jacsau.4c00300","DOIUrl":"10.1021/jacsau.4c00300","url":null,"abstract":"<p >To study the influence of heteroatoms on the photophysical properties of divalent Eu and Sr complexes, the synthesis of the phospholyl and arsolyl compounds [{(Dtp)(thf)M}<sub>2</sub>{μ-η<sup>8</sup>:η<sup>8</sup>-C<sub>8</sub>H<sub>8</sub>}] (M = Eu<sup>II</sup> and Sr<sup>II</sup>; Dtp = 3,4-dimethyl-2,5-bis(<i>tert</i>-butyl)phospholyl) and [{(Dtas)(thf)M}<sub>2</sub>{μ-η<sup>8</sup>:η<sup>8</sup>-C<sub>8</sub>H<sub>8</sub>}] (M = Eu<sup>II</sup> and Sr<sup>II</sup>; Dtas = 3,4-dimethyl-2,5-bis(<i>tert</i>-butyl)arsolyl) is reported. Organometallic compounds of divalent europium with P and As heterocyclic ligands have not been described previously. They were prepared by salt elimination reactions from potassium phospholyl or arsolyl, K<sub>2</sub>C<sub>8</sub>H<sub>8</sub>, and EuI<sub>2</sub>(thf)<sub>2</sub> or SrI<sub>2</sub>. Photophysical properties were investigated alongside a reference cyclopentadienyl complex with a comparable structure. Critically, the influence of the heteroatom on the photoluminescence emission and excitation and quantum yields of the complexes is significant. Density functional theory calculations were performed to rationalize the ligand influences.</p>","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":null,"pages":null},"PeriodicalIF":8.5,"publicationDate":"2024-06-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/jacsau.4c00300","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141376141","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
On-Surface Molecular Recognition Driven by Chalcogen Bonding 由链烷键驱动的表面分子识别
IF 8.5
JACS Au Pub Date : 2024-06-05 DOI: 10.1021/jacsau.4c00325
Luca Camilli*, Conor Hogan*, Deborah Romito, Luca Persichetti, Antonio Caporale, Maurizia Palummo, Marco Di Giovannantonio and Davide Bonifazi*, 
{"title":"On-Surface Molecular Recognition Driven by Chalcogen Bonding","authors":"Luca Camilli*,&nbsp;Conor Hogan*,&nbsp;Deborah Romito,&nbsp;Luca Persichetti,&nbsp;Antonio Caporale,&nbsp;Maurizia Palummo,&nbsp;Marco Di Giovannantonio and Davide Bonifazi*,&nbsp;","doi":"10.1021/jacsau.4c00325","DOIUrl":"10.1021/jacsau.4c00325","url":null,"abstract":"<p >Chalcogen bonding interactions (ChBIs) have been widely employed to create ordered noncovalent assemblies in solids and liquids. Yet, their ability to engineer molecular self-assembly on surfaces has not been demonstrated. Here, we report the first demonstration of on-surface molecular recognition solely governed by ChBIs. Scanning tunneling microscopy and <i>ab initio</i> calculations reveal that a pyrenyl derivative can undergo noncovalent chiral dimerization on the Au(111) surface through double Ch···N interactions involving Te- or Se-containing chalcogenazolo pyridine motifs. In contrast, reference chalcogenazole counterparts lacking the pyridyl moiety fail to form regular self-assemblies on Au, resulting in disordered assemblies.</p>","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":null,"pages":null},"PeriodicalIF":8.5,"publicationDate":"2024-06-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/jacsau.4c00325","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141382388","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
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