Chemistry - A European Journal最新文献_第10页

Charge-Segregated Ion-Pairing Assemblies Comprising Dipolar π-Electronic Cations.

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2025-02-07 DOI: 10.1002/chem.202404781

Kazuhisa Yamasumi, Hiroki Horita, Yohei Haketa, Shu Seki, Kirill Bulgarevich, Kazuo Takimiya, Hiroyuki Shimogawa, Hiromitsu Maeda

引用次数: 0

Ultrafast Photoinduced Electron Transfer Between Donor (Eosin-Y) and Acceptor (Naphthoquinone) in a Supramolecular Array Based on a Coordination Cage Host.

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2025-02-07 DOI: 10.1002/chem.202404647

Max B Tipping, Jack M Woolley, James R Williams, Michael D Ward

{"title":"Ultrafast Photoinduced Electron Transfer Between Donor (Eosin-Y) and Acceptor (Naphthoquinone) in a Supramolecular Array Based on a Coordination Cage Host.","authors":"Max B Tipping, Jack M Woolley, James R Williams, Michael D Ward","doi":"10.1002/chem.202404647","DOIUrl":"10.1002/chem.202404647","url":null,"abstract":"An octanuclear M8L12 coordination cage host (HPEG ⋅ M) in aqueous solution binds neutral electron-accepting guests such as naphthoquinone (NQ) in its central cavity via the hydrophobic effect, and multiple anionic photosensitisers such as Eosin-Y (EY2-) around the exterior surface due to 16+ charge on the complex cation: this is confirmed by both solution titration experiments and X-ray crystallography. In the three-component assembly HPEG ⋅ Cd/EY2 -/NQ, photoexcitation of EY2 - at 525 nm results in ultrafast (ca. 1 ps) photoinduced EY2-→NQ electron transfer from surface-bound EY2 - to cavity-bound NQ (which have been brought into close proximity by their interactions with different sites on the host cage) to give the charge-separated pair EY⋅-/NQ⋅-, identified by transient absorption spectroscopy: back-ET results in charge recombination in ≈70 ps. The assembly of donor and acceptor components via orthogonal interactions using the host cage as a scaffold presents a promising route into spatial control of multiple components in supramolecular arrays for photophysical applications.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202404647"},"PeriodicalIF":3.9,"publicationDate":"2025-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143363370","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

The Next Generation of Phosphorus Bisylide Superbases - Synthesis, Structures, Basicity and Proton Self-Exchange.

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2025-02-07 DOI: 10.1002/chem.202404692

Julius F Kögel, Sebastian Ullrich, Xiulan Xie, Lars H Finger, Borislav Kovačević, Jaan Saame, Tõiv Haljasorg, Ivo Leito, Jörg Sundermeyer

{"title":"The Next Generation of Phosphorus Bisylide Superbases - Synthesis, Structures, Basicity and Proton Self-Exchange.","authors":"Julius F Kögel, Sebastian Ullrich, Xiulan Xie, Lars H Finger, Borislav Kovačević, Jaan Saame, Tõiv Haljasorg, Ivo Leito, Jörg Sundermeyer","doi":"10.1002/chem.202404692","DOIUrl":"10.1002/chem.202404692","url":null,"abstract":"Herein we present two phosphorus ylide superbases to enhance the basicity of 1,8-bis (methylylidene (hexamethyltriamino) phosphorane) naphthalene (MHPN) - the first superbase with interacting carbon atoms as basicity centers. Its 1-pyrrolidinyl substituted analog 1,8-bis (methylylidene (tris (1-pyrrolidinyl)) phosphorane) naphthalene (MTPN) and MHPN's theoretically predicted higher homologue P2-MHPN exhibit extreme pKaH values of 26.0 and 29.5 (experimental) in THF solution and 33.6 and 37.4 (estimated) in acetonitrile solution. The corresponding calculated gas phase basicity values are 281.4 and 284.6 kcal mol-1, respectively. We prepared the neutral free bases together with the corresponding mono- and bisprotonated species which were characterized by NMR spectroscopy, ESI mass spectrometry, IR spectroscopy, elemental analysis and partly XRD analysis. The monoprotonated forms exhibit a rapid proton self-exchange between the two carbon atoms in peri-position and dynamic NMR spectroscopic methods revealed self-exchange rates of 2298 s-1 and 300 s-1 at 300 K for MTPN and P2-MHPN, respectively. However, computational studies reveal that the proton chelating effect, which typically considerably contributes to the basicity of proton sponges with basicity centers on nitrogen, is negligible in bisylides, as the 1,8-substitution pattern yields almost the same basicity as the corresponding 2,7- or 1,5-substituted analogues.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202404692"},"PeriodicalIF":3.9,"publicationDate":"2025-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143363369","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

Understanding the Nitrogen Reduction Reaction Mechanism on CuFeO2 Photocathodes.

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2025-02-07 DOI: 10.1002/chem.202500058

Julian Beßner, Timo Jacob

{"title":"Understanding the Nitrogen Reduction Reaction Mechanism on CuFeO2 Photocathodes.","authors":"Julian Beßner, Timo Jacob","doi":"10.1002/chem.202500058","DOIUrl":"https://doi.org/10.1002/chem.202500058","url":null,"abstract":"This study investigates the reaction pathways for the conversion of N2 to NH3 on CuFeO2 (CFO) by employing density functional theory (DFT) calculations. Concentrating on the most stable (012) surface orientation, two systems were examined: the pristine (012) surface and the corresponding oxygen defective surface. To find the thermodynamic stable pathway, the associative Heyrovský mechanism was considered, containing four different reaction pathways. The reaction intermediates predominantly interact with the iron sites on the surface, following the distal alternating reaction pathway via the formation of hydrazine. Introducing oxygen defects changes the reaction mechanism to a Mars-van-Krevelen-type mechanism, avoiding the formation of hydrazine, while the Gibbs free energy of the first hydrogenation step is lowered by 1.17 eV (from 2.17 to 1.00 eV). Analyzing the charge density distribution reveals that oxygen defective surface enables CFO to facilitate a π-backdonation between iron sites and the NRR intermediates, increasing the intermediate-surface interaction. This indicates an enhanced catalytic activity for the nitrogen reduction reaction (NRR) by generating oxygen lattice defects in CFO.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500058"},"PeriodicalIF":3.9,"publicationDate":"2025-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143370155","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

Kinetic Control and Trapping in the Supramolecular Polymerization of m-Terphenyl Bis-Urea Macrocycles.

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2025-02-07 DOI: 10.1002/chem.202404552

Gamage Isuri P Wijesekera, Isabella G Rushton, Vaibhavi A Samant, Fahidat A Gbadamosi, Md Faizul Islam, Mark D Smith, Shehani T Wetthasinghe, Sophya Garashchuk, Linda S Shimizu

{"title":"Kinetic Control and Trapping in the Supramolecular Polymerization of m-Terphenyl Bis-Urea Macrocycles.","authors":"Gamage Isuri P Wijesekera, Isabella G Rushton, Vaibhavi A Samant, Fahidat A Gbadamosi, Md Faizul Islam, Mark D Smith, Shehani T Wetthasinghe, Sophya Garashchuk, Linda S Shimizu","doi":"10.1002/chem.202404552","DOIUrl":"10.1002/chem.202404552","url":null,"abstract":"Herein, we examine pathway complexity in the supramolecular polymerization of a novel m-terphenyl bis-urea macrocycle. Designed to induce kinetically metastable states, the macrocycle's concentration-dependent aggregation was studied via 1H NMR and IR spectroscopy in THF and CHCl₃. Temperature-dependent UV-Vis spectroscopy in water/THF revealed a cooperative nucleation-growth mechanism, indicated by a shift in λmax to longer wavelengths upon cooling. Morphological studies using DLS, AFM, and SEM demonstrated fibrous aggregate formation. Thermal hysteresis observed in assembly-disassembly cycles indicated kinetically trapped species, with cooling governed by kinetic control and heating by thermodynamic processes. Deviations in ΔH values during cooling, compared to van't Hoff analysis and alignment of heating ΔH values with thermodynamic predictions, reinforced this distinction. Spontaneous nucleation retardation, resulting from monomer trapping, led to lag times of up to 50 minutes under specific conditions. Computational studies revealed the parallel urea conformation as the more stable monomer configuration, whereas the antiparallel conformation is more stable in dimers. By probing pathway complexity of the macrocycle, we demonstrate a distinct ability to control and stabilize kinetically trapped states, broadening the scope for designing macrocyclic supramolecular polymers with tailored properties. This work deepens our understanding of supramolecular dynamics, exploring ON-pathway mechanisms and advancing tunable supramolecular materials.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202404552"},"PeriodicalIF":3.9,"publicationDate":"2025-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143363365","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

Pt(II) Complexes Showing Multicolor Emissions from Nanoparticles in Solution and Reversible Grinding- and Heating-Induced Luminescence Switching in Solid State.

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2025-02-07 DOI: 10.1002/chem.202403886

Xin-Tong Lv, Dong Zheng, Fu-Shun Wan, Yi-Lei Liu, Zi-Hao Guo, Deng-Ke Cao, Xiao-Liang Yang

{"title":"Pt(II) Complexes Showing Multicolor Emissions from Nanoparticles in Solution and Reversible Grinding- and Heating-Induced Luminescence Switching in Solid State.","authors":"Xin-Tong Lv, Dong Zheng, Fu-Shun Wan, Yi-Lei Liu, Zi-Hao Guo, Deng-Ke Cao, Xiao-Liang Yang","doi":"10.1002/chem.202403886","DOIUrl":"10.1002/chem.202403886","url":null,"abstract":"To well understand luminescence modulation of Pt(II) complexes by inter-molecular interactions, three platinum complexes [Pt(moppy)Cl(L)] have been synthesized (Scheme 1) through incorporating the same C^N ligand moppyH=2-(4-methoxyphenyl)pyridine, while different auxillary ligands L: SEt2 in 1, iccy=isocyanocyclohexane in 2, and icna=isocyanonaphthalene in 3. Crystal structures indicate that neighbouring molecules are connected through π⋅⋅⋅π interactions, forming supramolecular dimer structures in both 1 and 2, while supramolecular chain structure in 3. In a CH3CN-H2O mixed solvent, complexes 1-3 reveal enhanced luminescence due to nanoparticle formation. Upon increasing water fraction from 0 % to 90 %, complex 1 exhibits increasing green luminescence with two broad emissions at 450 and 516 nm. In contrast, both 2 and 3 show multicolour emissions, transiting from blue to yellow-green for 2, and from blue green to orange red for 3. Moreover, complex 3 exhibits reversible luminescence switching between on state with orange-red emission and off state upon alternately grinding and heating. In this paper, we discuss the influences of molecular structures and inter-molecular π⋅⋅⋅π and Pt-Pt interactions on luminescence behaviours of complexes 1-3.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202403886"},"PeriodicalIF":3.9,"publicationDate":"2025-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143363368","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

Cover Feature: Mechanistical Study on Substrate-Controlled Highly Selective [2+2] and [2+3] Cycloaddition Reactions (Chem. Eur. J. 8/2025)

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2025-02-06 DOI: 10.1002/chem.202580803

Dr. Junbo Wang, Chuan Deng, Dr. Yong Zhang, Dr. Kaifeng Niu, Dr. Xinjing Zhao, Huaming Zhu, Yi Zhang, Dr. Peipei Huang, Prof. Dr. Haiping Lin, Prof. Dr. Jianchen Lu, Prof. Dr. Johanna Rosen, Prof. Dr. Jonas Björk, Prof. Dr. Jinming Cai, Prof. Dr. Qing Li

引用次数: 0

Structural Revision and Total Synthesis of Primarolides A and B via Massarinin A as a Common Precursor - Discovery of a Surprising 1,4-Aryl Shift.

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2025-02-06 DOI: 10.1002/chem.202404408

Marvin Schwamborn, Linus Stremmel, Jörg-Martin Neudörfl, Hans-Günther Schmalz

{"title":"Structural Revision and Total Synthesis of Primarolides A and B via Massarinin A as a Common Precursor - Discovery of a Surprising 1,4-Aryl Shift.","authors":"Marvin Schwamborn, Linus Stremmel, Jörg-Martin Neudörfl, Hans-Günther Schmalz","doi":"10.1002/chem.202404408","DOIUrl":"10.1002/chem.202404408","url":null,"abstract":"To probe the possible non-enzymatic formation of the polyketidic fungal metabolites primarolides A and B, the supposed 2-formyl-benzophenone precursor was prepared by chemical synthesis exploiting an anionic homo-Fries rearrangement to set up the highly substituted benzophenone unit. Conversion of this compound into the putative primarolides (i. e. the isomeric phthalide and the corresponding N-phenyl-isoindolinone) revealed that the proposed structures had to be revised. Subsequently, the natural product massarinin A, which displays a similar 2-formyl-benzophenone substructure, was synthesized following a related strategy. Treatment of massarinin A with Sc(OTf)3 or cyanide as a nucleophilic catalyst unexpectedly proceeded under 1,4-aryl migration to afford primarolide A. In contrast, reaction of massarinin A with aniline gave rise to primarolide B without aryl shift. All structural assignments were confirmed by X-ray crystal analysis and the proposed mechanism of the skeletal rearrangement was supported by 13C labeling. The study not only led to the total synthesis and structural revision of the primarolides but also supports the hypothesis of their non-enzymatic formation as racemates under the reported fermentation conditions, with the added suberoylanilide hydroxamic acid (SAHA) likely serving as the source of aniline.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202404408"},"PeriodicalIF":3.9,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143254111","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

Green Synthesis of Copper Nanoparticles utilising the Maillard Reaction.

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2025-02-06 DOI: 10.1002/chem.202404314

Lukas Mielewczyk, Virginia Liebscher, Julia Grothe, Stefan Kaskel

引用次数: 0

Electronic Interactions in Coulombic Associated Photoactive Macrocycles to Chemically Modified MoS₂ Nanosheets.

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2025-02-06 DOI: 10.1002/chem.202404746

Marina Tsigkou, Eleni Nikoli, Ioanna K Sideri, Michalis Kardaras, Hiram Joazet Ojeda Galvan, Mildred Quintana, Nikos Tagmatarchis

{"title":"Electronic Interactions in Coulombic Associated Photoactive Macrocycles to Chemically Modified MoS2 Nanosheets.","authors":"Marina Tsigkou, Eleni Nikoli, Ioanna K Sideri, Michalis Kardaras, Hiram Joazet Ojeda Galvan, Mildred Quintana, Nikos Tagmatarchis","doi":"10.1002/chem.202404746","DOIUrl":"10.1002/chem.202404746","url":null,"abstract":"Whilst functionalization of transition metal dichalcogenides (TMDs), and more specifically MoS2, has flourished the past decade, the accommodation of photoactive molecules on their lattice has unlocked the potentiality of this family of materials in a series of optoelectronic and energy related applications. The electronic communication between the chromophore and MoS2, in such systems, has been thoroughly studied, in cases where the grafting of the former on the latter is secured through covalent bonding. However, comparatively less attention has been drawn in cases where the chromophore is electrostatically anchored on MoS2, a means that potentially provides alternative ways of spatially accommodating the ligand on the TMD's extended environment, which directly affects the electronic communication between the two entities. In this work, we comparatively study the photophysical characteristics of three separate nanoensembles, where MoS2 is electrostatically hosting a Zn-phthalocyanine, a Zn-porphyrin, and a boron-dipyrromethene, that complementary cover a wide range of visible absorption, via UV-Vis and photoluminescence spectroscopy. The results highlight the strong interactions in the excited state across all chromophores, while the ground-state interactions vary from chromophore to chromophore, indicating a distinct energy exchange dependent on the specific nanoensemble.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202404746"},"PeriodicalIF":3.9,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143254107","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