Chemistry - A European Journal最新文献_第3页

Intersystem Crossing, Photo-Induced Charge Separation and Regioisomer-Specific Excited State Dynamics in Fully Rigid Spiro Rhodammine-Naphthalene/Anthraquinone Electron Donor-Acceptor Dyads. 完全刚性螺罗-罗丹明-萘/蒽醌电子施主-受主二元体中的系间交叉、光诱导电荷分离和区域异构体特异性激发态动力学。

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2024-11-20 DOI: 10.1002/chem.202403758

Kaiyue Ye, Andrey A Sukhanov, Jiayu Li, Lishan Liu, Xi Chen, Jianzhang Zhao, Violeta K Voronkova, MingDe Li

{"title":"Intersystem Crossing, Photo-Induced Charge Separation and Regioisomer-Specific Excited State Dynamics in Fully Rigid Spiro Rhodammine-Naphthalene/Anthraquinone Electron Donor-Acceptor Dyads.","authors":"Kaiyue Ye, Andrey A Sukhanov, Jiayu Li, Lishan Liu, Xi Chen, Jianzhang Zhao, Violeta K Voronkova, MingDe Li","doi":"10.1002/chem.202403758","DOIUrl":"https://doi.org/10.1002/chem.202403758","url":null,"abstract":"We prepared a series fully rigid spiro electron donor-acceptor orthogonal dyads, with closed form of rhodamine (Rho) as electron donor and naphthalene (Np)/anthraquinone (AQ) as electron acceptor, to access the long-lived triplet charge separation (3CS) state, via the electron spin control method. We found strong dependency of the photophysical property of the dyads on the amino substitution positions of the Np chromophores in the dyads 1,8-DaNp-Rho and 2,3-DaNp-Rho. Nanosecond transient absorption (ns-TA) spectra show the population of the 3LE state (lifetime: 47 μs) for 2,3-DaNp-Rho, however, long-lived 3CS state was observed (τCS = 0.62 μs) for AQ-Rho, with a CS quantum yield of ΦCS = 58%. Based on femtosecond transient absorption (fs-TA) spectra, spin orbit charge transfer ISC (SOCT-ISC) is proposed to be responsible for the formation of the triplet states. Time-resolved electron paramagnetic resonance (TREPR) spectra of AQ-Rho indicate the presence of two states, a 3LE state with zero field splitting (ZFS) D parameter of 1400 MHz and E parameter of -410 MHz, formed via radical pair ISC (RP-ISC) and SOCT-ISC mechanism; and a 3CS state with the electron spin-spin interaction in the regime of spin-correlated radical pair (SCRP).","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202403758"},"PeriodicalIF":3.9,"publicationDate":"2024-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142680289","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

Parts-per-million Level Loading Cyclometalated Ru(II)-NHC Catalyzed Selective Oxidation of Olefins to Carbonyls. 百万分率级负载环甲基化 Ru(II)-NHC 催化烯烃到羰基的选择性氧化。

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2024-11-19 DOI: 10.1002/chem.202403135

Monuranjan Konwar, Tapashi Das, Animesh Das

{"title":"Parts-per-million Level Loading Cyclometalated Ru(II)-NHC Catalyzed Selective Oxidation of Olefins to Carbonyls.","authors":"Monuranjan Konwar, Tapashi Das, Animesh Das","doi":"10.1002/chem.202403135","DOIUrl":"https://doi.org/10.1002/chem.202403135","url":null,"abstract":"Oxidative cleavage of olefins is a useful reaction in organic synthesis. The most well-known catalytic system is the osmium based Lemieux-Johnson catalyst, which generally requires high catalyst loading and tends to suffer from rapid overoxidation to produce the acid predominantly. Hence, the development of a mild, general, and selective method toward the oxidative cleavage of alkenes to carbonyl compounds is highly desired. In this work, a highly efficient ruthenium-based catalyst for olefin oxidation has been demonstrated by employing a fused π-conjugated imidazo[1,5-a]quinoxaline (ImQx) based NHC ligand with bidentate C(carbanion)^CNHC motif. Strong C-donor ligands, paired with a rigid backbone and ruthenium redox activity, provided exceptionally high catalytic activity and a long lifetime for olefin oxidation. Complex showed high catalytic activity and a long lifetime, TONs are several million. The catalyst tolerates numerous functional groups and can be applicable to challenging biomass, natural products, sugar, amino acids, and fatty acid-derived substrates. Based on kinetic studies, thermodynamic activation parameters, and DFT study, the mechanistic finding demonstrated that [3+2] cycloaddition reaction is the key step in the oxidation process. The use of the by-product NaIO3 in the catalytic efficiency has been disclosed for the first time.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202403135"},"PeriodicalIF":3.9,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142674643","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

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 : 2024-11-19 DOI: 10.1002/chem.202403749

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

引用次数: 0

In-situ reduced Cu3N nanocrystals enable high-efficiency ammonia synthesis and zinc-nitrate batteries. 原位还原 Cu3N 纳米晶体实现了高效氨合成和硝酸锌电池。

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2024-11-19 DOI: 10.1002/chem.202404129

Shanshan Chen, Zhiwei Wang, Quan Zhang, Shiming Qiu, Yifan Liu, Guangzhi Hu, Jun Luo, Xijun Liu

{"title":"In-situ reduced Cu3N nanocrystals enable high-efficiency ammonia synthesis and zinc-nitrate batteries.","authors":"Shanshan Chen, Zhiwei Wang, Quan Zhang, Shiming Qiu, Yifan Liu, Guangzhi Hu, Jun Luo, Xijun Liu","doi":"10.1002/chem.202404129","DOIUrl":"10.1002/chem.202404129","url":null,"abstract":"Nitrate reduction reaction (NO3RR) involves an 8-electron transfer process and competes with the hydrogen evolution reaction process, resulting in lower yields and Faraday efficiency (FE) in the process of NH3 synthesis. Especially, Cu-based catalysts (Cu0 and Cu+) have been investigated in the field of NO3RR due to the energy levels of d-orbital and the least unoccupied molecular orbital (LUMO) π* of nitrate's orbital. Based on the above, we synthesized a Cu-based compound containing Cu3N (Cu+) through a simple one-step pyrolysis method, applied it to electrocatalytic NO3RR, and tested the performance of the Zn-NO3- battery. Through various characterization analyses, Cu-based catalysts (Cu+) are the key active sites in reduction reactions, making Cu3N a potential catalyst for ammonia synthesis. The research results indicate the application of Cu3N catalyst in NO3RR shows the best NH3 yield of 173.7 μmol h-1 cm-2, with FENH3 reaching 91.0% at -0.3 V vs. RHE, which is much higher than that of Cu catalyst without N. In addition, the Zn-NO3- battery based on Cu3N electrode also exhibits an NH3 yield of 39.8 μmol h-1 cm-2, 63.0% FENH3, and a power density of 2.7 mW cm-2, as well as stable cycling charge-discharge stability for 5 hours.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202404129"},"PeriodicalIF":3.9,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142666526","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

Site-Selective γ-Trihalomethylation and γ-Dihalomethylidenation of Silyl Dienol Ethers under Organophotoredox Catalysis. 有机醛催化下硅烷二酚醚的γ-三卤甲基化和γ-二卤甲基亚甲基化的位点选择性。

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2024-11-19 DOI: 10.1002/chem.202403598

Camille Banoun, Fabien Bourdreux, Emmanuel Magnier, Guillaume Dagousset

引用次数: 0

Translating Solid-Phase Conformational Memory in the Prophecy of Multi-stimuli Responsive Low Molecular Weight Gels. 多刺激响应低分子量凝胶预言中的固相构象记忆转化。

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2024-11-19 DOI: 10.1002/chem.202403467

Bipul Sarma, Himanshu Sharma, Debabrat Pathak, Niharika Tanwar, Pankaj Tiwari

{"title":"Translating Solid-Phase Conformational Memory in the Prophecy of Multi-stimuli Responsive Low Molecular Weight Gels.","authors":"Bipul Sarma, Himanshu Sharma, Debabrat Pathak, Niharika Tanwar, Pankaj Tiwari","doi":"10.1002/chem.202403467","DOIUrl":"10.1002/chem.202403467","url":null,"abstract":"Polymorphism and its screening to select the best-performing form is in high demand. In low molecular weight organogels (LMWG), gelators are designed as they contain flexible groups, functionalities capable of varied H-bonding, and increased the potential to show polymorphism. We synthesized a bis-urea based LMWG G1 and isolated three distinct polymorphic phases (Form I, II, and III). G1 polymorphs showed noticeable differences in solubility; precisely, Form I is highly soluble compared to the other two. Gel screening was carried out for all three polymorphs using different stimuli like heat-cool, sonication, shaking, and grinding. Among the polymorphs, Form I was found to have better gelling ability which was reflected by the solvent scope, thermal stability (gel-sol transition temperature Tgel), minimum gelator concentration (M.G.C.), stimuli-responsiveness, morphology, and rheological properties. The differences in their gelation performance among the three polymorphs are associated with their solubility parameter. Stimuli like sonication, shaking, and grinding triggered Form I to form a gel. Form II and III responded to heat-cool stimuli only due to poor solubility. Therefore, it is noted crucial to add polymorph screening as an integral part of the gel synthesis to avoid problems associated with reproducibility in the gel prophecy of LMWG systems.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202403467"},"PeriodicalIF":3.9,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142666533","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

Metalized Borylene in Boron-Gold Carbonyl Complexes: Infrared Spectra and Theoretical Calculations. 硼金羰基复合物中的金属化硼烯：红外光谱和理论计算。

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2024-11-19 DOI: 10.1002/chem.202403368

Xuefeng Wang, Jin Hu

{"title":"Metalized Borylene in Boron-Gold Carbonyl Complexes: Infrared Spectra and Theoretical Calculations.","authors":"Xuefeng Wang, Jin Hu","doi":"10.1002/chem.202403368","DOIUrl":"https://doi.org/10.1002/chem.202403368","url":null,"abstract":"Borylenes (:B-R), built on a single B-R bond between boron and another nonmetallic atom or group, are a heated subject of special interest due to their intriguing transition-metal-mimicking reactivity, but the relative lack of understanding for the electronic structure and chemical bonding of transition metal borides leads to lingering neglect of metalized borylenes (:B-M) based on covalent B-M bonding. Here we use infrared photodissociation spectroscopy in combination with density functional calculations to study the geometric structure and chemical bonding of boron-gold carbonyl complex cations. The structure and bonding analyses demonstrated that the BAu(CO)3+ and BAu2(CO)4+ complexes can be described as bis-carbonyl-trapped borylene adducts. While the metal-rich BAu3(CO)4+ complex represents an unusual multicenter-bond-stabilized borylene cation with excellent σ-acidity and π-backbonding capability for CO activation, featuring Cs symmetry with a quasi-T-shaped BAu3+ core. It is manifested that BAu3+ presents greater amphoteric reactivity and improved stability compared to BAu1,2+ due to the presence of the three-center-two-electron Au-B-Au bond. This study discloses a conceptually new platform for accessing reactive metalized borylenes by exploiting the boron-mediated multicenter-bond stabilization strategy and using more bench-stable and ubiquitous metal carbonyl fragments as starting materials, thus providing a broader opportunity for the design of novel chemical structures and catalysts.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202403368"},"PeriodicalIF":3.9,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142674642","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

Magnetohydrodynamic Enhancement of Biofuel Cell Performance. 增强生物燃料电池性能的磁流体动力学。

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2024-11-19 DOI: 10.1002/chem.202403329

Gerardo Salinas, Tatjana Safarik, Marta Meneghello, Sabrina Bichon, Sebastien Gounel, Nicolas Mano, Alexander Kuhn

{"title":"Magnetohydrodynamic Enhancement of Biofuel Cell Performance.","authors":"Gerardo Salinas, Tatjana Safarik, Marta Meneghello, Sabrina Bichon, Sebastien Gounel, Nicolas Mano, Alexander Kuhn","doi":"10.1002/chem.202403329","DOIUrl":"10.1002/chem.202403329","url":null,"abstract":"Biofuel cells have become an interesting alternative for the design of sustainable energy conversion systems with multiple applications ranging from biosensing and bioelectronics to autonomously moving devices. However, as an electrochemical system, their performance is intimately related to mass transport conditions. In this work, the magnetohydrodynamic (MHD) effect is studied as an easy and straightforward alternative to enhance the performance of a biofuel cell based on the enzymes glucose oxidase (GOx) and bilirubin oxidase (BOD). The synergetic effect between the electric and ionic currents, produced by the enzymatic redox reactions, and a magnetic field orthogonal to the surface of the electrodes, leads to the formation of localized magnetohydrodynamic vortexes. Such an integrated convective regime generates an increase of the bioelectrocatalytic current and its concomitant power output in the presence of the external magnetic field. In addition, by fine-tuning the spatial arrangement of the anode and cathode, it is possible to benefit from the sum of anodic and cathodic MHD vortexes, leading to an enhanced power output of up to 300%.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202403329"},"PeriodicalIF":3.9,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142666527","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

Terphenyl-Ge as µ2-Ge-bis(hexahapto-Trip) Bridging Ligand to Form a New Transition Metal-Only Chelating Lewis Base. 三联苯-锗作为 µ2-Ge 双（六巯基-三）桥接配体，形成一种新的过渡金属螯合路易斯碱。

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2024-11-19 DOI: 10.1002/chem.202404201

Johanna Manegold, Adrian Ebisch, Klaus Eichele, Hartmut Schubert, Lars Wesemann

{"title":"Terphenyl-Ge as µ2-Ge-bis(hexahapto-Trip) Bridging Ligand to Form a New Transition Metal-Only Chelating Lewis Base.","authors":"Johanna Manegold, Adrian Ebisch, Klaus Eichele, Hartmut Schubert, Lars Wesemann","doi":"10.1002/chem.202404201","DOIUrl":"https://doi.org/10.1002/chem.202404201","url":null,"abstract":"Terphenylgermanium Ar*Ge [Ar* = C6H3(2,6-Trip)2, Trip = 2,4,6-C6H2iPr3] was found to act as a novel µ2-Ge-bis(hexahapto-Trip) bridging ligand. Deprotonated terphenyl germanium trihydride [Li(thf)3][Ar*GeH2] (1) undergoes reductive elimination and transfer of hydrogen in reaction with dimeric [(COD)RhCl]2 to yield the dinuclear complex [Ar*GeRh(COE)RhCl(COD)] (2). Subsequent chloride abstraction from compound 2 using Na[BArF4] or Li[Al(OtBuF)4] results in the cationic complexes [Ar*GeRh(COE)Rh(COD)][WCA] (3) {WCA : [BArF4]- (ArF = C6H3-3,5-(CF3)2), [Al(OtBuF)4]-}. Ligand exchange of olefin for CO yields the carbonyl complex [Ar*Ge(Rh(CO))2][BArF4] (4). In an alternative approach to the synthesis of carbonyl complex 4, [Li(thf)3][Ar*GeH2] (1) was treated with [Rh(CO)2Cl]2 leading to the isolation of a hexanuclear rhodium cluster [(µ3-Ar*Ge)2{Rh(CO)2}6(µ3-H)2] (5) in reasonable yield. In reactions with [Rh(CO)2Cl]2 or [Ph3PAuCl] complex 4 abstracts the chloride ligand and forms tetranuclear complexes featuring a GeRh3- or GeRh2Au-rectangle, [Ar*GeCl(Rh3(CO)4)][BArF4] (6), or [Ar*GeCl{Rh2(CO)2}(AuPPh3)][BArF4] (7).","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202404201"},"PeriodicalIF":3.9,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142674645","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

Dual-Coreactants Enhanced Electrochemiluminescence. 双核反应物增强电化学发光。

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2024-11-19 DOI: 10.1002/chem.202403804

Jialian Ding, Bin Su

引用次数: 0