Chemistry - A European Journal最新文献_第8页

Construction of Polydopamine@Crosslinked Polystyrene Core/Shell Polymeric Support for the Immobilization of Silver Nano-cluster: Adsorption and Selective Reduction of p-Chloronitrobenzene. Polydopamine@Crosslinked聚苯乙烯核壳聚合物载体固定化银纳米簇的构建：对氯硝基苯的吸附和选择性还原

IF 3.6 2区化学

Chemistry - A European Journal Pub Date : 2026-10-10 DOI: 10.1002/chem.71786

Jiwei Feng, Jian Shen, Zheng Cao, Tiantian Zhu, Jianli Wang

{"title":"Construction of Polydopamine@Crosslinked Polystyrene Core/Shell Polymeric Support for the Immobilization of Silver Nano-cluster: Adsorption and Selective Reduction of p-Chloronitrobenzene.","authors":"Jiwei Feng, Jian Shen, Zheng Cao, Tiantian Zhu, Jianli Wang","doi":"10.1002/chem.71786","DOIUrl":"https://doi.org/10.1002/chem.71786","url":null,"abstract":"Polymers are promising catalyst supports because of their tunable composition and facile functionality. In this work, a core/shell polydopamine@crosslinked polystyrene support (XP-PDA) was first constructed, and silver nano-clusters were subsequently immobilized via in situ reduction to yield Ag@XP-PDA. Adsorption kinetic and temperature-dependent isotherm tests were conducted to compare the adsorption capacity of the catalysts toward the reactant p-chloronitrobenzene (P-CNB) and its corresponding hydrogenation product p-chloroaniline (P-CAN). At 298 K, Ag@XP-PDA reached adsorption equilibrium within 180 min, with distinct capacities of 38.5 mg g-1 for P-CNB, whereas only 9.2 mg g-1 for P-CAN. Increasing the temperature from 298 to 318 K enhanced the adsorption capacity for P-CNB (from 50.3 to 54.1 mg g-1) while suppressing that for P-CAN (from 15.3 to 11.6 mg g-1). This distinct temperature-dependent adsorption behavior indicates the chemisorption of P-CNB for substrate enrichment. Improved substrate adsorption and product desorption endow Ag@XP-PDA with over 90% P-CAN chemoselectivity at 318 K. Hence, the XP-PDA support enables both the stabilization of Ag nano-clusters and enrichment of the substrate, affording an efficient catalytic system for the selective reduction of P-CNB to P-CAN.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e71786"},"PeriodicalIF":3.6,"publicationDate":"2026-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149147332","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

Excited-State Intramolecular Proton Transfer (ESIPT) Driven Emission Switching in a Coordination Polymer for Selective Detection of Nitroaniline Isomers. 配位聚合物中激发态分子内质子转移（ESIPT）驱动的发射开关用于硝基苯胺异构体的选择性检测。

IF 3.6 2区化学

Chemistry - A European Journal Pub Date : 2026-10-09 DOI: 10.1002/chem.71775

Anupam Maiti, Arijit Halder, Rakesh Kumar, Debajyoti Ghoshal

{"title":"Excited-State Intramolecular Proton Transfer (ESIPT) Driven Emission Switching in a Coordination Polymer for Selective Detection of Nitroaniline Isomers.","authors":"Anupam Maiti, Arijit Halder, Rakesh Kumar, Debajyoti Ghoshal","doi":"10.1002/chem.71775","DOIUrl":"https://doi.org/10.1002/chem.71775","url":null,"abstract":"Nitroaniline (NA) isomers are important, yet hazardous dye industry intermediates, require rapid and selective detection. Although conventional coordination polymers can detect NA through fluorescence quenching or wavelength shifting, however their limited signal discrimination often complicates the detection process. In this context, excited-state intramolecular proton transfer (ESIPT)-regulated emission switching offers distinct advantages by enabling dual-to-single emission transitions, visual color change, and improved analyte discrimination through the modulation of proton transfer pathways. Herein, an ESIPT-active Cd(II)-based coordination polymer has been synthesized using 2,5-dihydroxyterephthalate (dht) as an ESIPT-active ligand. The framework exhibits ESIPT-mediated dual emission in polar solvents, with the most pronounced response in water, producing intense yellow luminescence. Notably, exposure to aqueous solutions of NA isomers selectively perturbed the water-assisted ESIPT process, resulting in a distinct dual-to-single emission transition accompanied by fluorescence quenching and a readily noticeable visual color change from yellow to colorless. In contrast, other aromatic amines produced negligible disruption of the dual-emission response, highlighting the excellent selectivity of the sensing platform. Generalized-gradient-approximation-based DFT calculations by guest-induced modulation of competing proton-transfer pathways explain the observed ESIPT response. This study demonstrates that ESIPT-regulated dual-to-single emission switching can provide an advanced luminescent CP-based sensor for the selective detection and discrimination of nitroaniline isomers.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e71775"},"PeriodicalIF":3.6,"publicationDate":"2026-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149134455","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

Accelerating SCF Convergence Through Equivariant Density-Matrix Learning and Analytic Refinement. 用等变密度矩阵学习和解析精化加速SCF收敛。

IF 3.6 2区化学

Chemistry - A European Journal Pub Date : 2026-10-09 DOI: 10.1002/chem.71739

Zuriel Y Yescas-Ramos, Andrés Álvarez-García, Huziel E Sauceda

{"title":"Accelerating SCF Convergence Through Equivariant Density-Matrix Learning and Analytic Refinement.","authors":"Zuriel Y Yescas-Ramos, Andrés Álvarez-García, Huziel E Sauceda","doi":"10.1002/chem.71739","DOIUrl":"https://doi.org/10.1002/chem.71739","url":null,"abstract":"We present dm-PhiSNet, a physically constrained PhiSNet-based equivariant model that predicts one-electron reduced density matrices (1-RDMs) directly from molecular geometries in an atomic-orbital (AO) basis to accelerate self-consistent-field (SCF) convergence. Training follows a two-stage schedule with progressively introduced physically motivated objectives, and the resulting predictions are refined by a lightweight analytic block. This block enforces electron-number conservation, drives the 1-RDM toward generalized idempotency with respect to the AO overlap matrix <math><mi>S</mi></math> , and regularizes the occupation spectrum of the density matrix in an orthogonalized AO representation. Across six closed-shell systems- <math> <mrow><msub><mi>H</mi> <mn>2</mn></msub> <mi>O</mi></mrow> </math> , <math><msub><mi>CH</mi> <mn>4</mn></msub> </math> , <math><msub><mi>NH</mi> <mn>3</mn></msub> </math> , HF, ethanol, and <math><msubsup><mi>NO</mi> <mn>3</mn> <mo>-</mo></msubsup> </math> -the refined 1-RDMs provide SCF initial guesses that substantially reduce iteration steps by 49%-81% relative to standard initializations. Beyond SCF acceleration, the learned 1-RDMs yield accurate one-shot total energies and Hellmann-Feynman atomic forces without force supervision, indicating that the model captures chemically meaningful electronic structure. These results demonstrate that combining equivariant learning with analytic constraint enforcement provides a simple, general route to solver-ready density-matrix initializations and accelerated SCF calculations.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e71739"},"PeriodicalIF":3.6,"publicationDate":"2026-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149134513","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

Interface Issues and Optimization Strategies for Non-Lithium-Metal Anodes in All-Solid-State Batteries. 全固态电池中非锂金属阳极的界面问题与优化策略。

IF 3.6 2区化学

Chemistry - A European Journal Pub Date : 2026-10-09 DOI: 10.1002/chem.71769

Hao Chen, Yuan Zhou, Xiangxin Gu, Jihan Wu, Li Zhang

{"title":"Interface Issues and Optimization Strategies for Non-Lithium-Metal Anodes in All-Solid-State Batteries.","authors":"Hao Chen, Yuan Zhou, Xiangxin Gu, Jihan Wu, Li Zhang","doi":"10.1002/chem.71769","DOIUrl":"https://doi.org/10.1002/chem.71769","url":null,"abstract":"Unraveling the interface issues of non-lithium metal anodes (NLMAs) in all-solid-state batteries (ASSBs) and devising effective regulation strategies to enhance the rate and cycling performance has become a prominent research focus in both academia and industry. As promising anode candidates for high-energy-density ASSBs, NLMAs, including silicon-based, graphite-based, and tin-based anodes, offer unique advantages in terms of abundant natural resources, low cost, and superior safety. In recent years, significant progress has been made in addressing the interfacial issues of NLMAs in ASSBs. However, comprehensive reviews focusing on the interfacial challenges and corresponding optimization advances remain very rare. In response, this review first elucidates the intrinsic differences between solid-solid interfaces in ASSBs and traditional liquid-solid interfaces, thereby clarifying the typical characteristics of ideal interfaces for high-performance ASSBs. Subsequently, we systematically summarize various interface issues and the underlying failure mechanisms of NLMAs in practical applications, followed by a comprehensive overview of state-of-the-art interface optimization strategies and their working principles. Finally, the critical challenges of NLMA interface optimization are highlighted, and future research directions are prospected. This review provides in-depth insights into the failure mechanisms and optimization strategies of next-generation NLMAs and offers valuable resources for beginners in the field of ASSBs.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e71769"},"PeriodicalIF":3.6,"publicationDate":"2026-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149134509","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

Energetics of Proton-Coupled Electron Transfer in Hydroxy-Bridged Dicopper Complexes with N-Heterocyclic Carbene (NHC) Ligands. n-杂环卡宾（NHC）配体羟基桥接二铜配合物中质子耦合电子转移的能量学。

IF 3.6 2区化学

Chemistry - A European Journal Pub Date : 2026-10-09 DOI: 10.1002/chem.71780

Ning Ai, Xiao-Ming Wang, Yu-Hua Guo, Hong-Tao Zhang, Han Li, Ming-Tian Zhang

{"title":"Energetics of Proton-Coupled Electron Transfer in Hydroxy-Bridged Dicopper Complexes with N-Heterocyclic Carbene (NHC) Ligands.","authors":"Ning Ai, Xiao-Ming Wang, Yu-Hua Guo, Hong-Tao Zhang, Han Li, Ming-Tian Zhang","doi":"10.1002/chem.71780","DOIUrl":"https://doi.org/10.1002/chem.71780","url":null,"abstract":"A series of dinuclear μ-hydroxo bridged copper(II) complexes bearing N-heterocyclic carbene (NHC) ligands were designed to probe the ligand effect governing the activity patterns of particulate methane monooxygenase (pMMO). By systematically correlating experimental parameters (redox potentials E1/2 and acid dissociation constants pKa), we constructed stepwise thermodynamic frameworks that reveal a continuous O─H bond dissociation free energy (BDFEO-H) range spanning 68.5 to 106.7 kcal/mol in these copper-oxygen cores. Notably, while ligand substitution elicited only marginal variations in BDFEO-H when maintaining a fixed overall charge of Cu─O─Cu structure, modulation of the Cu─O─Cu core charge demonstrated superior efficacy over conventional steric/electronic ligand modifications for activating inert C─H bonds. Mechanistic studies revealed an efficient concerted electron-proton transfer (CEPT) pathway between the CuII─O─CuII and TEMPOH, achieving a remarkable second-order rate constant of 1745.4 M-1 s-1. This quantitative correlation between thermodynamic parameters and reaction kinetics provides fundamental principles for rational catalyst engineering.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e71780"},"PeriodicalIF":3.6,"publicationDate":"2026-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149147439","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

Mapping the Energy Landscape of Polycyclic Aromatic Hydrocarbon π-π Stacking Using a High-Precision Torsional Balance Based on the 13,14-Diphenyl-6,7-dihydrodibenzo[b,j][4,7]Phenanthroline Scaffold. 基于13,14-二苯基-6,7-二氢二苯并的高精度扭平衡多环芳烃π-π叠加能量格局绘制[b，j][4,7]。

IF 3.6 2区化学

Chemistry - A European Journal Pub Date : 2026-10-09 DOI: 10.1002/chem.71787

Chi-En Feng, Hsiu-Feng Lu, Chao-Ping Hsu, Chih-Hsiu Lin

{"title":"Mapping the Energy Landscape of Polycyclic Aromatic Hydrocarbon π-π Stacking Using a High-Precision Torsional Balance Based on the 13,14-Diphenyl-6,7-dihydrodibenzo[b,j][4,7]Phenanthroline Scaffold.","authors":"Chi-En Feng, Hsiu-Feng Lu, Chao-Ping Hsu, Chih-Hsiu Lin","doi":"10.1002/chem.71787","DOIUrl":"https://doi.org/10.1002/chem.71787","url":null,"abstract":"π-π stacking interactions are central to supramolecular assembly, material properties, and biomolecular organization. However, their intrinsically weak nature and sensitivity to geometric variation make them difficult to quantify experimentally. Here, we introduce a new molecular torsional balance based on a 13,14-diphenyl-6,7-dihydrodibenzo[b,j][4,7]phenanthroline (DHDBPT) scaffold that simultaneously achieves rotational restriction and conformational flexibility. This feature enables quantitative measurements of π-π interactions across multiple stacking geometries. Fluorine substituents are installed as a reliable probe for rotamer equilibria through integration of 19F NMR signals. Eighteen homodimeric and four heterodimeric torsional balances were synthesized and studied. Across the series of homo-stacked and hetero-stacked PAH dimers, the measured stabilizations range from 0.3 to over 2.0 kcal mol-1 and correlate strongly with interfacial π-surface overlap. These results demonstrate that dispersion dominates PAH stacking even in solution, while contributions from other interactions are secondary. The DHDBPT torsional balance offers an energetic resolution of ∼0.2 kcal mol-1 and structural resolution on the Å scale. It provides a general platform for interrogating weak noncovalent interactions with high precision.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e71787"},"PeriodicalIF":3.6,"publicationDate":"2026-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149147062","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

Structure-Activity Relationships in Methyl-Driven Overhauser Effect DNP. 甲基驱动Overhauser效应DNP的构效关系。

IF 3.6 2区化学

Chemistry - A European Journal Pub Date : 2026-10-09 DOI: 10.1002/chem.71772

Ananya Mukherji, Emma A Foley, Shubha S Gunaga, Thierry Dubroca, Mukaila A Ibrahim, Jin-Seok Yi, Nisreen Sharara, Syed Raza, Fadwat Bazzi, Simona Marincean, Dragos F Flesariu, Panayiotis A Koutentis, Frédéric Mentink-Vigier, Takeshi Kobayashi, Christos P Constantinides, Frédéric A Perras

{"title":"Structure-Activity Relationships in Methyl-Driven Overhauser Effect DNP.","authors":"Ananya Mukherji, Emma A Foley, Shubha S Gunaga, Thierry Dubroca, Mukaila A Ibrahim, Jin-Seok Yi, Nisreen Sharara, Syed Raza, Fadwat Bazzi, Simona Marincean, Dragos F Flesariu, Panayiotis A Koutentis, Frédéric Mentink-Vigier, Takeshi Kobayashi, Christos P Constantinides, Frédéric A Perras","doi":"10.1002/chem.71772","DOIUrl":"https://doi.org/10.1002/chem.71772","url":null,"abstract":"Dynamic nuclear polarization (DNP) enables dramatic sensitivity enhancements in solid-state nuclear magnetic resonance studies of materials. Most DNP approaches rely on the cross effect mechanism that typically employs nitroxide biradicals that are chemically incompatible with many samples and whose efficiency decreases with increasing magnetic field strength. The Overhauser effect DNP mechanism is a potential alternative that allows the use of a broader range of radical polarizing agents but requires further development. Mixed-valence and methyl-functionalized conjugated radicals have both been shown to enable Overhauser DNP, yet general design rules remain elusive. Here, we studied a series of 14 methyl-functionalized Blatter-type radicals to elucidate key structure-activity relationships. We found that radicals with sterically unhindered methyl groups are active, a feature readily identifiable from a Kekulé structure. Substitutions that alter molecular conformation, and thus the spin density distribution, predictably reduce performance. Addition of trifluoromethyl groups, commonly employed to enhance stability, also decreases activity by withdrawing spin density from Overhauser-active sites. These findings provide design principles that accelerate the discovery of efficient methyl-driven Overhauser effect DNP polarizing agents.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e71772"},"PeriodicalIF":3.6,"publicationDate":"2026-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149147224","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

Design and Synthesis of an Indoloquinoxaline Non-Fullerene Acceptor-Polythiophene Donor-Based Double Cable Polymer as an All-Organic Photocatalyst for Artificial Photosynthesis of H₂O₂. 吲哚喹啉非富勒烯受体-多噻吩给体双缆聚合物用于H2O2人工光合作用全有机光催化剂的设计与合成

IF 3.6 2区化学

Chemistry - A European Journal Pub Date : 2026-10-09 DOI: 10.1002/chem.71783

Faseeh Akbar, Sumbleen, Rameesa Sufi, Wajeeha Batool, Muhammad Subhan Shafi, Senem Çitoğlu, Sümeyye Sönmez, Muhammad Imran Malik, Hatice Duran, Raja Shahid Ashraf, Ljiljana Fruk, Basit Yameen

{"title":"Design and Synthesis of an Indoloquinoxaline Non-Fullerene Acceptor-Polythiophene Donor-Based Double Cable Polymer as an All-Organic Photocatalyst for Artificial Photosynthesis of H2O2.","authors":"Faseeh Akbar, Sumbleen, Rameesa Sufi, Wajeeha Batool, Muhammad Subhan Shafi, Senem Çitoğlu, Sümeyye Sönmez, Muhammad Imran Malik, Hatice Duran, Raja Shahid Ashraf, Ljiljana Fruk, Basit Yameen","doi":"10.1002/chem.71783","DOIUrl":"https://doi.org/10.1002/chem.71783","url":null,"abstract":"Excitons produced upon photoexcitation of organic semiconducting polymers (OSPs) are short lived, which limits their performance as photoactive materials. Exciton dissociation in OSPs can be enhanced by covalently conjugating them with acceptor species displaying higher electron affinity in a double cable polymer (DCP) arrangement, where non-fullerene acceptors (NFAs) are emerging as attractive alternatives. Herein, we report a new all-organic DCP comprising an electron donor polythiophene (PTh) covalently conjugated to an indoloquinoxaline (IQx) NFA (PTh-IQx-DCP). The selection of PTh and IQx as donor-acceptor pair is supported by the experimentally and theoretically determined favorable alignment of their band gaps and energies of HOMOs/LUMOs. The fluorescence and TRPL profiles reveal enhanced donor-acceptor electronic communication in PTh-IQx-DCP. PTh-IQx-DCP exhibits superior photoelectrochemical characteristics compared to P3HT, IQx, and P3HT+IQx physical hybrid (PH). As photocatalyst, PTh-IQx-DCP produces 906 ± 38 µM.mg-1 H2O2 cumulated over 10 photocatalytic cycles with a 10-cycles apparent average turnover frequency (TOF) of 3.5 h-1 and an apparent quantum yield (AQY) of 0.8% at 440 nm. The H2O2 production for PTh-IQx-DCP averaged over 10 photocatalytic cycles is 1.6, 3.4, and 1.4 times superior compared to P3HT, IQx, and P3HT+IQx PH, respectively. Overall, this work expands the molecular design space of DCPs based photoactive materials.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e71783"},"PeriodicalIF":3.6,"publicationDate":"2026-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149147121","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 and Reactivity of Substituted Phosphanylalanes and -Gallanes Stabilized by N-Heterocyclic Carbenes. n -杂环碳烯稳定取代磷酰三烷和-加仑烷的合成及其反应性。

IF 3.6 2区化学

Chemistry - A European Journal Pub Date : 2026-10-09 DOI: 10.1002/chem.71781

Tatiana N Parfeniuk, Michael Weinhart, Christoph Riesinger, Manfred Scheer

{"title":"Synthesis and Reactivity of Substituted Phosphanylalanes and -Gallanes Stabilized by N-Heterocyclic Carbenes.","authors":"Tatiana N Parfeniuk, Michael Weinhart, Christoph Riesinger, Manfred Scheer","doi":"10.1002/chem.71781","DOIUrl":"https://doi.org/10.1002/chem.71781","url":null,"abstract":"A series of N-heterocyclic carbene (NHC)-stabilized phosphanylgallanes and highly temperature sensitive phosphanylalanes bearing aliphatic and aromatic substituents at the phosphorus atom were synthesized via salt metathesis reactions of IDipp-coordinated (IDipp = 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene) triel halide precursors with alkali metal phosphanides. The gallium derivatives IDipp∙GaH2PHtBu (1) and IDipp∙GaH2P(tBu)2 (2) were isolated and structurally characterized, revealing monomeric species with distorted tetrahedral coordination at the group 13 element. The corresponding aluminum compounds IDipp·AlEt2PHtBu (3), IDipp·AlEt2PHPh (4), IDipp·AlEt2PPh2 (5), and IDipp·AlEt2PH2 (6) exhibit a strong dependence of their electronic and structural properties on the substitution pattern at the phosphorus atoms. X-ray diffraction studies show that Al─P bonds in the P atom substituted phosphanylalanes are elongated compared to IDipp·AlEt2PH2. Furthermore, computational analysis of the frontier molecular orbitals revealed the availability of the phosphorus lone pair. Comparison of donor abilities of the studied compounds with known substituted phosphanylboranes also indicates that these phosphanylalanes and -gallanes can serve as strong σ donating ligands. The reactivity of phosphanylgallanes toward SMe2·BH3 with formation of IDipp·GaH2PPh2·BH3 (9) and IDipp·GaH2PH2·BH3 (10), respectively, confirms the accessibility of the phosphorus lone pair and highlights their potential as Lewis base compounds.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e71781"},"PeriodicalIF":3.6,"publicationDate":"2026-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149147467","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

A Low-Oxidation-State Mechanism for O─O Bond Formation in Photosystem II via Oxo-Hydroxyl Radical Coupling. 光系统II中氧-羟基自由基偶联形成O─O键的低氧化态机制

IF 3.6 2区化学

Chemistry - A European Journal Pub Date : 2026-10-08 DOI: 10.1002/chem.71765

Alireza Ariafard, Matthew Longhurst, Robert Stranger

{"title":"A Low-Oxidation-State Mechanism for O─O Bond Formation in Photosystem II via Oxo-Hydroxyl Radical Coupling.","authors":"Alireza Ariafard, Matthew Longhurst, Robert Stranger","doi":"10.1002/chem.71765","DOIUrl":"https://doi.org/10.1002/chem.71765","url":null,"abstract":"In this computational work, we identify an oxo-hydroxyl radical coupling (OHC) mechanism for O─O bond formation in PSII within the low-oxidation-state (LOS) paradigm, in which the Ca-bound W3 water and O5 act as the substrates. While several recent crystallographic and computational studies indicate that the Ox ligand is absent in the S3 state, we show that it forms upon entry into the S4 state through migration of the Ca-bound water ligand W3 into the cavity between Mn1 and Ca2 +. From this intermediate, Ox─O5 bond formation proceeds via the OHC mechanism rather than the conventional oxo-oxyl pathway. This mechanism leads to formation of a hydroperoxide intermediate as the lowest-energy post-coupling species, in which Mn1 is reduced to the III oxidation state. Jahn-Teller distortion considerably weakens the Mn1(III)─Ox bond, explaining the poor resolution of Ox in XFEL structures following O─O bond formation, an observation difficult to reconcile within conventional high-oxidation-state (HOS) models. Importantly, the proposed mechanism is consistent with water-exchange experiments identifying W3 and O5 as the substrate oxygen atoms. The mechanistic insights obtained in this work enabled us to propose likely S state structures and proton-release assignments within the Kok cycle.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e71765"},"PeriodicalIF":3.6,"publicationDate":"2026-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149134517","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