Chemical Science最新文献_第6页

Exploring the Excited State Mechanisms of a Viscosity-Sensitive Zeromethine Merocyanine Dye Emitter 粘度敏感零甲基Merocyanine染料发射器激发态机制的探索

IF 8.4 1区化学

Chemical Science Pub Date : 2026-10-12 DOI: 10.1039/d6sc05772a

Julian Fichtner,Preetika Verma,Menyhárt B Sárosi,Matthias Stolte,Adithya Lakshmanna Yapamanu,Frank Würthner

{"title":"Exploring the Excited State Mechanisms of a Viscosity-Sensitive Zeromethine Merocyanine Dye Emitter","authors":"Julian Fichtner,Preetika Verma,Menyhárt B Sárosi,Matthias Stolte,Adithya Lakshmanna Yapamanu,Frank Würthner","doi":"10.1039/d6sc05772a","DOIUrl":"https://doi.org/10.1039/d6sc05772a","url":null,"abstract":"Merocyanine (MC) dyes are among the most versatile and tunable chromophores owing to their structural flexibility. However, their excited state dynamics often leading to fluorescence quenching by ultrafast non-radiative decay pathways such as photoisomerization or relaxation through conical intersections are poorly understood for most MCs. Herein, we elucidate the excited state mechanisms of a zeromethine MC dye (PyBA), which represents a special case of the donor-acceptor architecture featuring two directly connected heterocycles. The analysis was achieved by combining steady-state measurements under varying temperature, viscosity and polarity conditions, time-resolved ultrafast spectroscopy, and quantum-chemical calculations. Our studies show that PyBA upon photoexcitation develops a twisted intramolecular charge transfer (TICT) state in dynamic environments (e.g., CH2Cl2), whereas this process is restricted in rigid environments (PMMA matrix), leading to a significant luminescence turn-on with the quantum yield (ΦPL) increasing from 0.7% to 55%. Moreover, the measurements performed in PMMA matrix reveal room temperature phosphorescence (RTP) even under ambient conditions, i.e. even without external stimuli, which becomes more intense at cryogenic temperatures under argon atmosphere, reaching a phosphorescence lifetime of 705 ms. Furthermore, it introduces a simple and time-efficient strategy for screening small-molecule fluorescence probes.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"12 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151876","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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

Phosphoric acid-etched boron nitride as a single-atom support for boosting CO2 electroreduction at high current density 磷酸蚀刻氮化硼作为单原子载体，在高电流密度下促进CO2电还原

IF 8.4 1区化学

Chemical Science Pub Date : 2026-10-12 DOI: 10.1039/d6sc06494a

Xuan Li,Yu-Ting Wang,Wei-Zhen Deng,Qian-Run Tan,Hong-Mei Liu,Wen-Juan Huang,Li-Dong Wang,Zi-Xuan Wu,Yuan-Jing Suo,Yan-Tong Xu,Li-Ming Cao,Hai-Hua Huang,Chun-Ting He

{"title":"Phosphoric acid-etched boron nitride as a single-atom support for boosting CO2 electroreduction at high current density","authors":"Xuan Li,Yu-Ting Wang,Wei-Zhen Deng,Qian-Run Tan,Hong-Mei Liu,Wen-Juan Huang,Li-Dong Wang,Zi-Xuan Wu,Yuan-Jing Suo,Yan-Tong Xu,Li-Ming Cao,Hai-Hua Huang,Chun-Ting He","doi":"10.1039/d6sc06494a","DOIUrl":"https://doi.org/10.1039/d6sc06494a","url":null,"abstract":"Designing adjustable and robustness support materials remains a critical challenge for enhancing the industrial-level CO2 electroreduction performance of single-atom catalysts. Herein, we report a defective and phosphate-modified boron nitride (BN) support via a facile phosphoric acid etching strategy to anchor single nickel atoms. The optimized electrocatalyst delivers an outstanding maximum CO Faradaic efficiency of 97.6 ± 1.2% in H-cell, and a large CO partial current density of 148.6 ± 2.3 mA·cm−2 in the gas diffusion electrode-based flow cell, which maintains high CO selectivity during 87 h of stable operation. A variety of characterizations including operando spectroscopy combined with theoretical calculations reveal that phosphoric acid etching redistributes the electronic structures of interface as well as Ni centers, which significantly optimize the *CO adsorption. Moreover, the surface phosphate species may play a critical role on stabilizing the key *COOH intermediate. This work not only provides a support material for achieving performance gain of transition metal single atoms, but also offers new insights into the interfacial molecule-mediated CO2 electrochemical conversion.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"41 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151875","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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

Thermally activated delayed fluorescence in neutral and cationic stages of aza-nanographene decorated with 6.6.6 defects. 含6.6.6缺陷的氮杂纳米石墨烯在中性和阳离子阶段的热激活延迟荧光。

IF 8.1 1区化学

Chemical Science Pub Date : 2026-10-09 DOI: 10.1039/d6sc06038b

Rohith Valavil Suku, Illia E Serdiuk, Krzysztof Dzieszkowski, Łukasz Orzeł, Monika Kijewska, Tadeusz M Muzioł, Miłosz Siczek, Miłosz Pawlicki

{"title":"Thermally activated delayed fluorescence in neutral and cationic stages of aza-nanographene decorated with 6.6.6 defects.","authors":"Rohith Valavil Suku, Illia E Serdiuk, Krzysztof Dzieszkowski, Łukasz Orzeł, Monika Kijewska, Tadeusz M Muzioł, Miłosz Siczek, Miłosz Pawlicki","doi":"10.1039/d6sc06038b","DOIUrl":"https://doi.org/10.1039/d6sc06038b","url":null,"abstract":"Heteroatom-doped polycyclic aromatic hydrocarbons (PAHs) show substantially modified electron distribution caused by the presence of either an electron-rich or electron-poor element that significantly influences the optical properties of final molecules. A novel synthetic approach with a PBr3 coupling agent, applied to precisely designed monomers and followed by intramolecular fusion, incorporates a tetraaza-dibenzo[g,p]chrysene decorated with two 6.6.6 defects into a nanographene-like system. The final derivative shows an efficient green fluorescence emission (λ PF = 530 nm) accompanied by phosphorescence (λ phos = 565 nm). The emission is tuned with simple protonation and shifted bathochromically to λ PF = 620 nm and λ phos = 640 nm. Both forms show thermally activated delayed fluorescence (TADF) with PLQYs of 93% for the green band and 50% for the red one, showing a unique ability to sustain the TADF behaviour after protonation.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":8.1,"publicationDate":"2026-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13678670/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149223423","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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

Toward resolving the RuO₂/IrO₂ oxygen evolution activity puzzle: critical roles of spin polarization and exchange-correlation functional accuracy. 解决RuO2/IrO2析氧活性难题：自旋极化和交换相关功能精度的关键作用。

IF 8.1 1区化学

Chemical Science Pub Date : 2026-10-09 DOI: 10.1039/d6sc04703c

Xiaokun Xie, Jiashun Wu, Zhenbin Wang

{"title":"Toward resolving the RuO2/IrO2 oxygen evolution activity puzzle: critical roles of spin polarization and exchange-correlation functional accuracy.","authors":"Xiaokun Xie, Jiashun Wu, Zhenbin Wang","doi":"10.1039/d6sc04703c","DOIUrl":"10.1039/d6sc04703c","url":null,"abstract":"The oxygen evolution reaction (OER) activity ordering of RuO2 and IrO2 is well established experimentally, yet density functional theory calculations have persistently failed to reproduce this trend, undermining computational catalyst design. Here, we investigate this discrepancy by evaluating OER thermodynamic and kinetic activities of IrO2 and RuO2 using four exchange-correlation (XC) functionals (PBE, RPBE, r2SCAN, and MS2-rVV10) under spin-polarized and spin-unpolarized conditions. Spin polarization selectively stabilizes the O* intermediate on IrO2 while leaving RuO2 comparatively unaffected, and neglecting spin effects yields unphysically low kinetic barriers for IrO2. Among the four functionals, only MS2-rVV10 reproduces the experimentally observed activity trend in both thermodynamic and kinetic analyses. We trace these failures to a systematic correlation between adsorption-energy errors and deviations in the predicted activity trend. Notably, the OOH*-OH* scaling offset and theoretical limiting potential are themselves XC-functional dependent, cautioning against cross-functional comparison of overpotentials. Cross-code benchmarks rule out numerical implementation as the error source, while higher-rung functionals progressively overestimate Ru local magnetic moments in RuO2, introducing additional errors. This work establishes accurate exchange-correlation functionals and proper spin-polarization treatment as prerequisites for reliable OER catalyst design.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":8.1,"publicationDate":"2026-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13673306/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149215099","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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

Realizing a 4,3,3-connected tfe topology in an imidazole-linked three-dimensional covalent organic framework. 在咪唑连接的三维共价有机框架中实现4,3,3连接的tfe拓扑结构。

IF 8.1 1区化学

Chemical Science Pub Date : 2026-10-09 DOI: 10.1039/d6sc06024b

Tsukasa Irie, Sourav Ghosh, Hayato Orui, Tokuhisa Kawawaki, Tasuku Hamaguchi, Hiroshi Jinnai, Ranjit Thapa, Saikat Das, Yuichi Negishi

{"title":"Realizing a 4,3,3-connected tfe topology in an imidazole-linked three-dimensional covalent organic framework.","authors":"Tsukasa Irie, Sourav Ghosh, Hayato Orui, Tokuhisa Kawawaki, Tasuku Hamaguchi, Hiroshi Jinnai, Ranjit Thapa, Saikat Das, Yuichi Negishi","doi":"10.1039/d6sc06024b","DOIUrl":"10.1039/d6sc06024b","url":null,"abstract":"Reticular chemistry relies on translating molecular geometry into periodic topology, yet many theoretically possible nets remain inaccessible because low-symmetry multinodal connectivity is difficult to crystallize. Here we report TU-433, an imidazole-linked three-dimensional covalent organic framework that realizes the first tfe topology COF and, to our knowledge, the first 4,3,3-connected reticular framework in either COFs or MOFs. Through topological simplification, an 8-connected aldehyde node and a trigonal 3-connected amine node evolve into a trinodal network containing one 4-connected and two crystallographically distinct 3-connected vertices. Crystallographic analysis, porosity measurements, spectroscopy, microscopy, electrochemical characterization, and computational modeling establish a non-interpenetrated crystalline framework with permanent microporosity, exceptional aqueous stability, polarized imidazole-rich pore environments, and measurable charge-transport capability derived from its conjugated heteroaromatic backbone. Beyond topological novelty, TU-433 functions as a robust adsorbent for anionic pollutants, delivering the highest reported Acid Orange 7 uptake among known adsorbents, together with efficient capture of Cr(vi) and Mn(vii) oxo-anions, regenerability, and activity in real textile wastewater. Mechanistic studies reveal that proton-responsive imidazole sites, π-rich pore walls, and confinement within the tfe lattice cooperate to drive adsorption. This work expands the accessible topology landscape of COFs and demonstrates how unprecedented connectivity can be coupled to practical water-remediation function.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":8.1,"publicationDate":"2026-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13670037/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149214970","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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

Beyond the catalytic serine: selective protease engagement with covalent macrocyclic activity-based probes. 超越催化丝氨酸：选择性蛋白酶参与共价大环活性为基础的探针。

IF 8.1 1区化学

Chemical Science Pub Date : 2026-10-09 DOI: 10.1039/d6sc04245g

Marina Barrueco, Ellie Hyde, Ella Sawtell, Jack V Mills, Vaia Nikoloudi, Marianne Enget, Maisem Laabei, Markus Lakemeyer, Scott Lovell

{"title":"Beyond the catalytic serine: selective protease engagement with covalent macrocyclic activity-based probes.","authors":"Marina Barrueco, Ellie Hyde, Ella Sawtell, Jack V Mills, Vaia Nikoloudi, Marianne Enget, Maisem Laabei, Markus Lakemeyer, Scott Lovell","doi":"10.1039/d6sc04245g","DOIUrl":"https://doi.org/10.1039/d6sc04245g","url":null,"abstract":"Activity-based probes (ABPs) are widely used to profile serine protease activity - enzymes central to diverse physiological and pathological processes - but most rely on covalent modification of the conserved catalytic serine residue, often resulting in poor selectivity across related proteases. Here, we introduce covalent macrocyclic activity-based probes (cmABPs) that selectively target non-catalytic residues within serine protease active sites. By combining phage display with systematic electrophile scanning, we identify macrocyclic scaffolds that position sulfur(vi) fluoride (SuFEx) electrophiles to covalently engage alternative nucleophiles such as lysine and tyrosine. Applied to plasma kallikrein, this approach yielded a macrocyclic scaffold that was converted into covalent probes via fluorosulfate scanning. Remarkably, small changes in electrophile structure produced large, tuneable differences in covalent kinetics, with benzenesulfonyl fluoride derivative 23 achieving rapid and complete protein modification. Biochemical and mass spectrometry analyses confirmed selective modification of an active-site lysine by 23, along with robust performance in complex biological samples. Extension to urokinase plasminogen activator further demonstrates the generality of this strategy. More broadly, this work establishes electrophile scanning within macrocyclic scaffolds as a general approach for tuning covalent reactivity and provides a blueprint for designing selective probes that move beyond catalytic-residue targeting.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":8.1,"publicationDate":"2026-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13659818/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149179655","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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

Noble gas electrochemistry-driven luminescence integrated with machine learning for environmental monitoring. 稀有气体电化学驱动发光与环境监测机器学习相结合。

IF 8.1 1区化学

Chemical Science Pub Date : 2026-10-09 DOI: 10.1039/d6sc04632k

Ziyu Wang, Wenxuan Zhao, Qiao Sun, Yulin Li, Chengqi Li, Meiyun Xu, Jing-Juan Xu, Daoben Hua

{"title":"Noble gas electrochemistry-driven luminescence integrated with machine learning for environmental monitoring.","authors":"Ziyu Wang, Wenxuan Zhao, Qiao Sun, Yulin Li, Chengqi Li, Meiyun Xu, Jing-Juan Xu, Daoben Hua","doi":"10.1039/d6sc04632k","DOIUrl":"https://doi.org/10.1039/d6sc04632k","url":null,"abstract":"Noble gases are traditionally known as not being easily involved in chemical reactions owing to their stable electronic configuration. Here, we study the electrochemical redox and electrochemiluminescence (ECL) mechanisms of a series of noble gases (radon, xenon and krypton) for the first time and demonstrate their ability to produce an ECL signal with an emission peak in the range of 600-640 nm. Among them, the key intermediates Rn˙+/Xe˙+ are observed via HPLC-MS to confirm their electrochemical redox and ECL process. Additionally, the anodic/cathodic ECL behavior and the ECL intensity of radon in an annihilation state are confirmed to depend on the interaction between solvent molecules and Rn˙-/Rn˙+, which can be summarized as a free radical-solvent interaction-dependent ECL (FSDE) mechanism. A machine learning framework with SHapley additive exPlanations analysis is also integrated to enable high-fidelity differentiation of Rn/Xe for accurate determination. This work advances our knowledge of the electrochemistry of noble gases and develops a machine-learning-assisted trace radon/xenon monitoring method with high selectivity and sensitivity. The ECL behavior is successfully employed for noble gas determination in various real-world atmospheric samples, indicating its application potential in the fields of environment, geoscience, and public health.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":8.1,"publicationDate":"2026-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13650928/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149165106","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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

Emergent integration of the amine scrubbing method into photocatalytic CO₂ reduction. 胺洗涤法在光催化CO2还原中的应用。

IF 8.1 1区化学

Chemical Science Pub Date : 2026-10-08 DOI: 10.1039/d6sc05488a

Naoki Hosokawa, Shunya Uno, Hiroharu Watanabe, Osamu Ishitani

{"title":"Emergent integration of the amine scrubbing method into photocatalytic CO2 reduction.","authors":"Naoki Hosokawa, Shunya Uno, Hiroharu Watanabe, Osamu Ishitani","doi":"10.1039/d6sc05488a","DOIUrl":"https://doi.org/10.1039/d6sc05488a","url":null,"abstract":"Developing strategies for photocatalytic reduction of low-concentration CO2 under ambient conditions is essential for mitigating global warming and addressing energy and carbon resource shortages. The amine scrubbing method (ASM), which captures dilute CO2 as carbamic acid using low-cost primary and secondary amines, is widely employed to generate concentrated CO2. However, releasing CO2 from carbamic acid to generate highly concentrated CO2 requires high-temperature heating, resulting in substantial energy consumption and cost. Herein, we report the integration of ASM with photocatalytic CO2 reduction. A newly synthesized complex [Ru(bpy)(P-P)(CO)(H)]+ (Ru-H+; bpy = 2,2'-bipyridine, P-P = Ph2PC2H4PPh2) serves as an efficient catalyst for reducing CO2 at low concentrations, even below 0.34%, in the presence of an Ir-based photosensitizer and a reductant (TONHCOOH ≥ 1925, Φ HCOOH = 39%, selectivityHCOOH > 97%). This system quantitatively converts CO2 captured by amines such as monoethanolamine into formic acid at room temperature. In this process, CO2 released from carbamic acid in solution is rapidly consumed via photocatalytic reduction, enabling efficient utilization of low-concentration CO2 without requiring energy-intensive regeneration processes.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":8.1,"publicationDate":"2026-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13662752/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149191597","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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

Polymer-bridging energy transfer enables full-color erasable room-temperature phosphorescence with high stability in aqueous environments. 聚合物桥接能量转移使全彩可擦除室温磷光具有高稳定性的水环境。

IF 8.1 1区化学

Chemical Science Pub Date : 2026-10-08 DOI: 10.1039/d6sc06597j

Dongbo Chen, Jiaxing Zhang, Jiaxue Ren, Jianzhong Fan, Jinzhu Ma, Henggang Wang, Zhenguang Wang, Andrey L Rogach

{"title":"Polymer-bridging energy transfer enables full-color erasable room-temperature phosphorescence with high stability in aqueous environments.","authors":"Dongbo Chen, Jiaxing Zhang, Jiaxue Ren, Jianzhong Fan, Jinzhu Ma, Henggang Wang, Zhenguang Wang, Andrey L Rogach","doi":"10.1039/d6sc06597j","DOIUrl":"10.1039/d6sc06597j","url":null,"abstract":"Achieving full-color, erasable, and stable photoactivated room-temperature phosphorescence (RTP) is often hindered by inefficient intersystem crossing, rapid triplet quenching and a low driving force for oxygen consumption, especially for deep-blue and red emissions. Herein, full-color photoactivated RTP materials, with ultralong emission lifetimes up to 4.18 s and reversibility over multiple write-erase cycles, are fabricated by doping organic phosphors into a polyvinyl butyral (PVB) polymer matrix. Unlike conventional inert hosts, PVB acts as an active energy transfer bridge that enhances host-guest energy transfer, promotes intersystem crossing and facilitates efficient oxygen consumption across a broad spectral range of 430-670 nm. The resulting films exhibit excellent stability in humid, acidic, alkaline, and saline environments, as well as full recyclability. Leveraging these properties, erasable photopatterning across multiple colors and scales, including large-area (20 × 20 cm) and fine-feature (2 mm) patterns, is demonstrated. Our results provide a general strategy to overcome key limitations in light-responsive RTP materials for dynamic anti-counterfeiting and rewritable data storage.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":8.1,"publicationDate":"2026-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13670511/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149214983","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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

Quantifying U-H covalency in a series of uranyl borohydrides using ¹H NMR spectroscopy. 用1H核磁共振光谱定量一系列铀酰硼氢化物的U-H共价。

IF 8.1 1区化学

Chemical Science Pub Date : 2026-10-08 DOI: 10.1039/d6sc04701g

C A U Kawshalya Kumarihami, Nathan R Loutsch, Nadia Arsenijevic, Guang Wu, Bess Vlaisavljevich, Trevor W Hayton

{"title":"Quantifying U-H covalency in a series of uranyl borohydrides using 1H NMR spectroscopy.","authors":"C A U Kawshalya Kumarihami, Nathan R Loutsch, Nadia Arsenijevic, Guang Wu, Bess Vlaisavljevich, Trevor W Hayton","doi":"10.1039/d6sc04701g","DOIUrl":"10.1039/d6sc04701g","url":null,"abstract":"The reaction of [UO2(OTf)2(Cy3PO)2] (1) with 2.4 equiv. of NaBH4 in THF affords [UO2(κ2-BH4)2(Cy3PO)2] (2) as yellow blocks in moderate isolated yield. Similarly, reaction of [UO2Cl2(THF)3] with 1 equiv. of [K(DME)2(H2-9-BBN)]2 ([H2-9-BBN]- = dihydrido 9-boratabicyclo-[3.3.1]nonane) in Et2O yields [UO2(κ2-H2-9-BBN)2(Et2O)2] (3) in moderate yields. Subsequent reaction of 3 with 1.8 equiv. of Cy3PO in toluene results in formation of [UO2(κ2-H2-9-BBN)2(Cy3PO)2] (4). Complexes 1-4 were characterized by X-ray crystallography, multinuclear NMR spectroscopy, and IR spectroscopy. The 1H NMR spectra for complexes 2, 3, and 4 exhibit significantly downfield shifted resonances for their hydride environments. This deshielding is due to strong spin-orbit effects arising from orbital interactions between the uranium center and the borohydride ligands. Density functional theory (DFT) calculations accurately reproduced the experimental chemical shifts and revealed that the uranium contribution to the U-H-B molecular orbitals ranged from 11-14%, depending on the complex, of which approximately 40% was due to the 5f orbitals.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":8.1,"publicationDate":"2026-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13673240/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149215028","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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