Chemistry - A European Journal最新文献_第4页

Stepwise Construction of Supramolecular A₂B₄-Type Miktoarm Star Copolymers with a Cobalt Phthalocyanine Core. 逐步构建以酞菁钴为核心的超分子 A2B4 型 Miktoarm 星型共聚物。

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2025-01-27 Epub Date: 2024-11-28 DOI: 10.1002/chem.202403749

Xinhao Zhong, Hsu-Tzu Cheng, Chu-Chen Chueh, Masayuki Takeuchi, Junko Aimi

引用次数: 0

Iridium/Acid-Dual Catalyzed Enantioselective Intramolecular Allylic Dearomatization Reaction of Allylic Alcohol Tethered α- and β-Naphthols. 铱/酸双催化α-和β-萘酚系链烯丙基醇的不对称分子内烯丙基脱芳烃反应。

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2025-01-27 Epub Date: 2024-11-28 DOI: 10.1002/chem.202403664

Amit Shikari, Subhas Chandra Pan

引用次数: 0

Flipping the Metalation of 4-Dimethylaminopyridine: Steric Repulsion versus London Dispersion Attraction. 4-Dimethylaminopyridine 的金属化翻转：立体斥力与伦敦分散吸引力。

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2025-01-27 Epub Date: 2024-11-26 DOI: 10.1002/chem.202403422

Valery A Verkhov, Alexandra N Gubanova, Daria I Tonkoglazova, Elena Yu Tupikina, Alexander S Antonov

{"title":"Flipping the Metalation of 4-Dimethylaminopyridine: Steric Repulsion versus London Dispersion Attraction.","authors":"Valery A Verkhov, Alexandra N Gubanova, Daria I Tonkoglazova, Elena Yu Tupikina, Alexander S Antonov","doi":"10.1002/chem.202403422","DOIUrl":"10.1002/chem.202403422","url":null,"abstract":"Non-covalent interactions, including the coordination of an organolithium reagent by a directing group and the steric hindrance from substituents, play a crucial role in determining the selectivity of metalation reactions. Here, we demonstrate the effective utilization of steric interactions for flipping the lithiation of 4-dimethylaminopyridine (DMAP). Introduction of a Me3Si substituent to the position 1 of DMAP or simple complexation with t-BuLi allows selective C3-lithiation, due to the steric hindrance of a C2-H bond by the bulky moiety at the pyridine nitrogen. This simple approach creates a convenient way to achieve the selective C3-functionalization of DMAP. In contrast, the utilization of an even bulkier i-Pr3Si substituent leads to exclusive C2-functionalization due to the dispersion interactions with organometallic bases. For the first time, it is demonstrated that the i-Pr3Si moiety can serve as a directing group, providing a new type of directed ortho-metalation effect.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202403422"},"PeriodicalIF":3.9,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11771546/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142613200","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

Cu(I)-Catalyzed Silylation and Germylation of Azauracils. Cu(I)-Catalyzed Silylation and Germylation of Azauracils.

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2025-01-27 Epub Date: 2024-11-18 DOI: 10.1002/chem.202403685

Frenki Mahato, Asim Kumar Ghosh, Alakananda Hajra

引用次数: 0

Visible-Light-Induced ArC(sp³)-F Bond Activation in Aqueous Media: From DFT Study to Molecular Design. 水介质中可见光诱导的ArC(sp3)-F键活化：从DFT研究到分子设计。

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2025-01-27 Epub Date: 2024-12-17 DOI: 10.1002/chem.202403729

Cefei Zhang, Sitong Li, Lijun Deng, Jinmeng Yan, Zhishan Su, Zhipeng Yu, Changwei Hu

{"title":"Visible-Light-Induced ArC(sp3)-F Bond Activation in Aqueous Media: From DFT Study to Molecular Design.","authors":"Cefei Zhang, Sitong Li, Lijun Deng, Jinmeng Yan, Zhishan Su, Zhipeng Yu, Changwei Hu","doi":"10.1002/chem.202403729","DOIUrl":"10.1002/chem.202403729","url":null,"abstract":"Trifluoromethylarenes (ArCF3) are crucial bioisosteres in medicinal chemistry, but catalyst-free and controlled photo-activation of the ArC(sp3)-F bond remains a significant challenge. The photo-induced defluorination acyl fluoride exchange (photo-DAFEx) of m-trifluoromethylaniline, induced by ultraviolet light, emerges as a promising novel photo-click reaction for photoaffinity drug discovery. However, the photophysical properties of NMe2PhF2C(sp3)-F derivatives and factors affecting ArC(sp3)-F bond activation in photo-DAFEx are not yet fully understood, hindering the development of new photo-defluorination reagents with longer absorption wavelength for the photo-DAFEx. Herein, the photophysical properties, the related mechanism and their affecting factors of a series of ArCF3 compounds are systematically studied using (TD)DFT methods. The skeleton of aromatic core is found to be intimately related to the absorption wavelength needed for ArC(sp3)-F bond activation. A photo-induced intramolecular single-electron activation model was proposed to rationalize the photo-activation of the ArC(sp3)-F bond. The transfer of excited electron to C(sp3)-F antibonding orbital determined the activation. Based on the above knowledge, three novel ArCF3 reagents with extended excitation wavelength were designed and predicted, and the absorption spectra and photo-defluorination reactivity of two of them with visible absorption wavelength were validated experimentally, which provided a theoretical guidance for designing next-generation photo-DAFEx.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202403729"},"PeriodicalIF":3.9,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142798686","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

Higher Assemblies of Coordination Cage-Catenanes Linked by Copper(II) Chloride Clusters: Networks and Transformations. 由铜（II）氯化物簇连接的高配位笼型链烷：网络和转化。

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2025-01-27 Epub Date: 2024-12-19 DOI: 10.1002/chem.202403692

Matthew P Snelgrove, Natalia N Sergeeva, Michaele J Hardie

{"title":"Higher Assemblies of Coordination Cage-Catenanes Linked by Copper(II) Chloride Clusters: Networks and Transformations.","authors":"Matthew P Snelgrove, Natalia N Sergeeva, Michaele J Hardie","doi":"10.1002/chem.202403692","DOIUrl":"10.1002/chem.202403692","url":null,"abstract":"Cage-catenanes are chemical constructs where two or more cage-like molecules or assemblies are mechanically interlocked together. We report a new class of cage-catenanes where dimeric metal-organic cage-catenanes are linked into larger assemblies through additional bridging metal chloride links. These crystalline materials are obtained from the reaction of tris(nicotinoyl)cyclotriguaiacylene (L1) with Cu(II) salts, and all feature a tetramer of cages where two {Cu3(L1)2(X)6} cages (X=anion) are mechanically interlocked, and link to each other and to another {Cu3(L1)2(X)6}2 cage-catenane through a planar, linear tetranuclear {Cu4(μ-Cl)6Cl2} cluster. The complex of discrete tetrameric {Cu3(L1)2(X)6}4 assemblies (dimers of cage-catenanes) transforms through solvent-exchange processes to 1D coordination chain structures through additional {Cu2(μ-Cl)2} bridges between the tetrameric {Cu3(L1)2(X)6}4 assemblies. Complex [Cu6(L1)4Cl12(H2O)3] ⋅ (H2O) ⋅ 15(DMF) C2 features a 2D coordination network of 63 topology linked through three different Cu(II) clusters, namely {Cu4(μ-Cl)6}, {Cu2(μ-Cl)2} and a rare linear {Cu2(μ-Cl)} linkage. Break-down of C2 in water likely proceeds through hydrolysis of this unusual linear Cu-Cl-Cl bond.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202403692"},"PeriodicalIF":3.9,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142826745","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

Impact of Double-π-Bridge on Bis(Triarylamine)-Based Organic Mixed-Valence System: A Case Study of Diaza[1.1](4,4")ortho-Terphenylophane Radical Cation. 双π桥对双（三芳胺）基有机混价体系的影响：以Diaza[1.1]（4,4”）邻苯二甲酸基阳离子为例

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2025-01-27 Epub Date: 2025-01-09 DOI: 10.1002/chem.202403945

Koshi Yoshida, Fumiya Takasaki, Masashi Uebe, Shu Seki, Akihiro Ito

引用次数: 0

Photoinduced Deprotection of 2-Nitrophenylneopentyl Glycol Boronates Enables Light-Triggered Polycondensation of Siloxanes. 光诱导脱保护的2-硝基苯基新戊二醇硼酸盐使光触发的硅氧烷缩聚。

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2025-01-27 Epub Date: 2025-01-09 DOI: 10.1002/chem.202404577

Marion Boyet, Boris Colin, Guillaume Michaud, Emilie Genin, Sandra Pinet, Laurent Chabaud, Mathieu Pucheault

{"title":"Photoinduced Deprotection of 2-Nitrophenylneopentyl Glycol Boronates Enables Light-Triggered Polycondensation of Siloxanes.","authors":"Marion Boyet, Boris Colin, Guillaume Michaud, Emilie Genin, Sandra Pinet, Laurent Chabaud, Mathieu Pucheault","doi":"10.1002/chem.202404577","DOIUrl":"10.1002/chem.202404577","url":null,"abstract":"Various protecting groups have been developed for boronic acids, mostly based on diols. Alternatives include trifluoroborates and amine complexes, which offer easier synthesis and release under milder conditions. We present here a new strategy involving photocleavable protecting groups for boronic and borinic acids, based on the 2-nitrobenzyl motif. A screening of several 1,2- and 1,3-diols bearing a 2-nitrobenzyl group led us to identify 1-(2-nitrophenyl)neopentyl glycol (npnp) for the protection of boronic acid derivatives. This diol is easily prepared in a single step on gram scale, and the corresponding npnp boronates are stable in wet acetonitrile at 90 °C for several days, and under under acidic conditions. Irradiation at 365 nm in acetonitrile allows for the controlled liberation of boronic acids in good to excellent yields, a method also applied to a dimesitylborinic ester bearing a 2-nitrobenzylalcohol moiety. 1-(2-Nitrophenyl)neopentyl glycol boronates ArB(npnp) demonstrated their utility in light-triggered siloxane crosslinking. We showed that catalysts incorporated into a polymer matrix, irradiated, and then incubated at 50 °C for 7 days resulted in efficient polymerization, forming solid materials in some cases.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202404577"},"PeriodicalIF":3.9,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142880775","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

Controlled Self-assembly of Nanographdiynes Mediated by Molecular Dipoles Induced by Rotatory Asymmetric Substituents.

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2025-01-27 DOI: 10.1002/chem.202404275

Jing Chen, Jingyi He, Xingzhong Wu, Yongjun Li

{"title":"Controlled Self-assembly of Nanographdiynes Mediated by Molecular Dipoles Induced by Rotatory Asymmetric Substituents.","authors":"Jing Chen, Jingyi He, Xingzhong Wu, Yongjun Li","doi":"10.1002/chem.202404275","DOIUrl":"https://doi.org/10.1002/chem.202404275","url":null,"abstract":"The discrete π- stacks of specific lengths and orientation is crucial for understanding the impact of intermolecular interactions on optical or electronic properties of nanographdiynes. We designed and synthesized nanographdiynes modified with bulky rotatable asymmetric substituents. The peripheral substituents with different push-pull electronic properties can induce molecular dipoles perpendicular to nanoGDY π surface with different orientation. Mediated by directional dipole-dipole interactions, o-TBGDY substituted with electron-donating tert-butylphenyl groups cofacially dimerized with a twist angle, involving intermolecular interlocking of ortho-substituted tert-butylphenyl groups. In contrast, OTFGDY substituted with electron-withdrawing trifluorophenyl groups formed dimeric H-aggregates with an in-plane shift along one diyne linkage, in which the ortho-substituted trifluorophenyl groups point toward the outside of the interacting π-plane. o-TBGDY can only exist as isolated H-dimer in the solid state, while OTFGDY can form a hybrid tetramer of H- and J-aggregates. Our researches reveal a new method for preparing discrete π-stacked dye assemblies with well-defined optoelectronic properties.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202404275"},"PeriodicalIF":3.9,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143044954","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

Synthesis of Bis(diimino)palladium Nanosheets as Highly Active Electrocatalysts for Hydrogen Evolution. 高效析氢电催化剂双（二亚胺）钯纳米片的合成。

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2025-01-27 Epub Date: 2024-12-06 DOI: 10.1002/chem.202403082

Hiroaki Maeda, Eunice Jia Han Phua, Yuta Sudo, Sayoko Nagashima, Wentai Chen, Mayumi Fujino, Kenji Takada, Naoya Fukui, Hiroyasu Masunaga, Sono Sasaki, Kazuhito Tsukagoshi, Hiroshi Nishihara

{"title":"Synthesis of Bis(diimino)palladium Nanosheets as Highly Active Electrocatalysts for Hydrogen Evolution.","authors":"Hiroaki Maeda, Eunice Jia Han Phua, Yuta Sudo, Sayoko Nagashima, Wentai Chen, Mayumi Fujino, Kenji Takada, Naoya Fukui, Hiroyasu Masunaga, Sono Sasaki, Kazuhito Tsukagoshi, Hiroshi Nishihara","doi":"10.1002/chem.202403082","DOIUrl":"10.1002/chem.202403082","url":null,"abstract":"Development of efficient electrocatalysts for hydrogen evolution reactions (HERs) is necessary to achieve environmentally friendly and sustainable hydrogen production. To reduce cost and to circumvent the scarcity of platinum, the most efficient catalyst for HER, it is essential to develop catalysts using ubiquitous base metals or minimal amounts of precious metals. Bis(diimino)metal (MDI) coordination nanosheets are potential HER catalysts because their electric conductivities, two-dimensionality, and porous structures provide large surface areas and efficient mass and electron transfer. In addition, with sparse metal arrangements in their chemical structures, nanosheets can reduce the amount of metal needed. We synthesized bis(diimino)palladium coordination nanosheets (PdDI) as a coordination polymer composed of bis(diimino)palladium, with semiconducting characteristics, using gas-liquid interfacial synthesis and electrochemical oxidation. These electrochemically synthesized PdDIs exhibit remarkable catalytic performance with overpotential reaching 10 mA cm-2 of 34 mV, a Tafel slope of 47 mV dec-1, and an exchange current density of 2.1 mA cm-2 after appropriate activation. This performance is closely comparable to that of metallic platinum. An ex-situ investigation of the activation process revealed that reduction of the divalent Pd center in bis(diimino)palladium produced a composite of Pd(0) species and PdDI, combining high catalytic activity with smooth electron transfer.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202403082"},"PeriodicalIF":3.9,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11771586/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142749438","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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