Dalton Transactions最新文献_第6页

Stability and Quantum Tunnelling in the Intramolecular Proton Transfer of Molybdic Acid 钼酸分子内质子转移的稳定性和量子隧道效应

IF 4 3区化学

Dalton Transactions Pub Date : 2026-10-13 DOI: 10.1039/d6dt02247b

Sebastian Kozuch,Julián Santoyo-Flores,Yeshayahu Ben-Eliyahu

{"title":"Stability and Quantum Tunnelling in the Intramolecular Proton Transfer of Molybdic Acid","authors":"Sebastian Kozuch,Julián Santoyo-Flores,Yeshayahu Ben-Eliyahu","doi":"10.1039/d6dt02247b","DOIUrl":"https://doi.org/10.1039/d6dt02247b","url":null,"abstract":"We explored with computational means the stability and interconversion kinetics of several possible molybdenum complexes in neutral or slightly acidic media, including, among others, [MoO(OH)4(H2O)], [MoO2(OH)2(H2O)2], [MoO(OH)4], and [MoO3(H2O)]. These complexes are related through three kinds of intramolecular proton-transfer reactions, allowing to convert one complex into another. In particular, we analysed the role of quantum tunnelling at low and high temperatures, with and without an explicit water molecule catalysing the reactions through a Grotthuss type of proton shuttle mechanism. We identified [MoO2(OH)2(H2O)2], compound 4, as the most stable structure, in line with previous studies. At room temperature all the interconversions are fast, allowing the system to readily reach compound 4 from every other possible complex; in these conditions, thermally activated tunnelling is a measurable but small factor. However, our results indicate that at low temperatures tunnelling is the only plausible mechanism for the reaction, permitting the fast rearrangements to reach compound 4 even in the absence of enough thermal energy to overcome the barriers.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"46 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149152692","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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

Construction of ternary methoxy hydroxide M(OH)(OCH₃) (M = Co, Cu, Mn) with a flower-like structure for highly efficient electrocatalytic oxygen evolution. 花状结构三元甲氧基氢氧化物M(OH)(OCH3) （M = Co, Cu, Mn）高效电催化析氧的构建

IF 3.3 3区化学

Dalton Transactions Pub Date : 2026-10-13 DOI: 10.1039/d6dt01680d

Pan Yang, Congmin Fan, Tiancheng Feng, Haoyu Peng, Yiming Xian

引用次数: 0

Synthesis of a labile CAAC-based diazoalkene: formation of a C4-cumulene and a head-to-tail dimer 一种不稳定的caac基重氮烯烃的合成：c4 -积云烯和首尾二聚体的形成

IF 4 3区化学

Dalton Transactions Pub Date : 2026-10-13 DOI: 10.1039/d6dt02166b

Vasu Malhotra,Arindam Mal,Priyanka Sarkar,Ramapada Dolai,Siva Murthy Bandaru,Cem B. Yildiz,Carola Schulzke,Anukul Jana

引用次数: 0

Post-synthetic lanthanide chelation enables radioluminescence in robust nanoscale MOFs. 合成后的镧系元素螯合可以在坚固的纳米mof中实现放射发光。

IF 3.3 3区化学

Dalton Transactions Pub Date : 2026-10-13 DOI: 10.1039/d6dt01662f

Megan J Neufeld, Elani Cabrera-Vega, Aireth LaVigne, Eunseo Choi, Yulan Ren, Theresa M McCormick, Andrea M Goforth, Guillem Pratx, Conroy Sun

{"title":"Post-synthetic lanthanide chelation enables radioluminescence in robust nanoscale MOFs.","authors":"Megan J Neufeld, Elani Cabrera-Vega, Aireth LaVigne, Eunseo Choi, Yulan Ren, Theresa M McCormick, Andrea M Goforth, Guillem Pratx, Conroy Sun","doi":"10.1039/d6dt01662f","DOIUrl":"10.1039/d6dt01662f","url":null,"abstract":"Materials capable of converting ionizing radiation into optical emission have been widely explored for imaging and radiation detection, yet the introduction of radioluminescence into chemically modular systems remains less well understood. Here, we report a modular strategy for introducing radioluminescence into chemically robust nanoscale MOFs through post synthetic lanthanide coordination. To our knowledge, this represents one of the first demonstrations of radioluminescence introduced into MOFs via post-synthetic lanthanide coordination. Using the zirconium-based framework UiO-66-(COOH)2 as a stable scaffold, coordination of Eu3+ and Tb3+ ions yields dispersible lanthanide-chelated MOF nanoparticles that retain crystallinity and nanoscale morphology while exhibiting characteristic lanthanide-centered emission under X-ray excitation. Lanthanide incorporation results in enhanced radioluminescent intensity and improved spectral definition relative to the undoped framework, with Tb-chelated materials displaying stronger emission consistent with more efficient linker-to-lanthanide energy transfer. Comparison of photoluminescent and radioluminescent behavior suggests that linker-mediated sensitization plays an important role in lanthanide-centered emission, while additional radioluminescence-specific processes may also contribute under X-ray excitation. Because these systems are designed for nanoscale dispersion and imaging-relevant configurations, this study emphasizes radioluminescent signal generation and spectral characteristics rather than detector-level metrics. Collectively, these results establish post-synthetic lanthanide chelation as a generalizable approach for engineering radioluminescence into robust MOF platforms and expand the accessible design space for X-ray responsive MOF materials.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" ","pages":"14086-14096"},"PeriodicalIF":3.3,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149079020","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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 Study on the Selectivity in 5-Hydroxymethylfurfural Reduction using SnO2-decorated Ru Catalysts: Unveiling the Importance of Furan Ring Aromaticity sno2修饰Ru催化剂还原5-羟甲基糠醛的选择性研究：揭示呋喃环芳香性的重要性

IF 4 3区化学

Dalton Transactions Pub Date : 2026-10-13 DOI: 10.1039/d6dt01596d

Adrián García-Zaragoza,Christian Cerezo-Navarrete,C. Marini,Ruben Laplaza,Pascual Oña-Burgos,Luis Miguel (M.) Martínez-Prieto

{"title":"A Study on the Selectivity in 5-Hydroxymethylfurfural Reduction using SnO2-decorated Ru Catalysts: Unveiling the Importance of Furan Ring Aromaticity","authors":"Adrián García-Zaragoza,Christian Cerezo-Navarrete,C. Marini,Ruben Laplaza,Pascual Oña-Burgos,Luis Miguel (M.) Martínez-Prieto","doi":"10.1039/d6dt01596d","DOIUrl":"https://doi.org/10.1039/d6dt01596d","url":null,"abstract":"The selective transformation of biomass-derived platform molecules into value-added chemicals requires catalysts capable of controlling the competition between hydrogenation and hydrodeoxygenation (HDO) pathways. Herein, graphene-supported Ru nanoparticles (RuNPs) were modified through a surface organometallic chemistry (SOMC) approach using tributyltin hydride (Bu3SnH), generating surface SnO2 species on the Ru NPs, as supported by XPS and XAS analyses. The catalytic performance of the resulting Ru@rGO/SnO2(x) materials (x = 0.5, 0.8 and 1 equiv.) was investigated in the reduction of 5-hydroxymethylfurfural (HMF). Unmodified Ru@rGO exhibited high hydrogenation activity, achieving 97.9 % conversion with 94 % selectivity towards 2,5-bis(hydroxymethyl)furan (BHMF) after 3 h and complete conversion to 2,5-bis(hydroxymethyl)tetrahydrofuran (BHMTHF) after 20 h. In contrast, the progressive incorporation of SnO2 species modified the product distribution by suppressing the hydrogenation of the aromatic furan ring while promoting HDO. As a result, Ru@rGO/SnO2(1) completely inhibited the formation of hydrogenated furan-ring products, reaching 97.7 % selectivity to 2,5-dimethylfuran (DMF) at extended reaction times. Combined adsorption studies, control experiments and computational calculations revealed that HDO processes only occur when the aromaticity of the furan ring is preserved. Once the ring is hydrogenated, the resulting products preferentially adsorb on the graphene support and become inactive towards further hydrodeoxygenation. These findings demonstrate that surface SnO2 species provide an effective strategy to tune the selectivity of Ru NPs and unveil the key role of furan-ring aromaticity in governing hydrodeoxygenation processes of biomass-derived molecules.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"18 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149152693","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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

Pyridine-Iminophosphorane earth-abundant metal complexes: Synthesis and Application in catalytic ketone hydrosilylation 吡啶-亚磷磷烷类富土金属配合物的合成及其在酮硅氢化催化中的应用

IF 4 3区化学

Dalton Transactions Pub Date : 2026-10-13 DOI: 10.1039/d6dt02274j

Laureen Busson,Sophie Bourcier,Nicolas Casaretto,Corinne Gosmini,Audrey Auffrant

引用次数: 0

KZrF5 and K 5Zr3F17•H2O: Two Zr-Containing Fluorides with Low Birefringence and Broad Transparency Range KZrF5和k5zr3f17•H2O：两种低双折射、宽透明范围的含锆氟化物

IF 4 3区化学

Dalton Transactions Pub Date : 2026-10-13 DOI: 10.1039/d6dt02348g

Ning Ye,Guang Peng,Wenhua Fu,Zhiyong Xue,Xin Wen,Xuemei Shi,Jindong Chen,Zhanggui Hu,Jiyang Wang

引用次数: 0

Interfacial electron redistribution in a TiO₂/Mn₃O₄ hollow heterostructure for selective photocatalytic CO₂-to-CO conversion. TiO2/Mn3O4中空异质结构中选择性光催化CO2-to-CO转换的界面电子重分布。

IF 3.3 3区化学

Dalton Transactions Pub Date : 2026-10-13 DOI: 10.1039/d6dt01800a

Yuanyuan Cheng, Xinyue Zhang, Jingwen Yu, Yunliang Liu, Yi Yang, Yishen Li, Xin Huang, Zhiquan Lang, Yixian Liu, Naiyun Liu, Xiang Liu, Yong Zhao, Haitao Li

{"title":"Interfacial electron redistribution in a TiO2/Mn3O4 hollow heterostructure for selective photocatalytic CO2-to-CO conversion.","authors":"Yuanyuan Cheng, Xinyue Zhang, Jingwen Yu, Yunliang Liu, Yi Yang, Yishen Li, Xin Huang, Zhiquan Lang, Yixian Liu, Naiyun Liu, Xiang Liu, Yong Zhao, Haitao Li","doi":"10.1039/d6dt01800a","DOIUrl":"10.1039/d6dt01800a","url":null,"abstract":"Selective photocatalytic CO2-to-CO conversion remains challenging because of rapid charge recombination and insufficient CO2 activation. Herein, a TiO2/Mn3O4 hollow heterostructure was constructed through a SiO2 hard-template strategy combined with in situ growth. The hollow hemispherical architecture provides an open and accessible structural platform for the in situ growth of Mn3O4 nanosheets and the construction of intimate TiO2/Mn3O4 heterointerfaces. Uniformly anchored Mn3O4 nanosheets establish intimate heterointerfaces that induce interfacial electron redistribution and promote charge separation. As a result, TiO2/Mn3O4 exhibits a CO evolution rate of 9.31 μmol g-1 h-1, which is 1.62 and 2.20 times higher than those of pristine TiO2 and Mn3O4, respectively, together with a CO selectivity of 84.03%, an electron selectivity of 56.81%, and excellent cycling stability. X-ray photoelectron spectroscopy analysis reveals pronounced interfacial electronic redistribution between TiO2 and Mn3O4, while photoelectrochemical measurements demonstrate enhanced charge separation and interfacial charge transfer. In situ diffuse reflectance infrared Fourier transform spectroscopy further confirms the preferential formation of *COOH and *CO intermediates, favoring the selective two-electron CO2-to-CO conversion pathway. This work demonstrates that regulating interfacial electron redistribution through hollow heterostructure engineering is an effective strategy for achieving efficient and selective photocatalytic CO2-to-CO conversion.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" ","pages":"14255-14263"},"PeriodicalIF":3.3,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149072858","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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

Electrifying Oxygen Atom Transfer Reactions: Utilizing OER and ORR Pathways for Organic Synthesis 通电氧原子转移反应：利用OER和ORR途径进行有机合成

IF 4 3区化学

Dalton Transactions Pub Date : 2026-10-13 DOI: 10.1039/d6dt01709f

Helena Pletsch,Kilaparthi Sravan Kumar,Dominik P. Halter

{"title":"Electrifying Oxygen Atom Transfer Reactions: Utilizing OER and ORR Pathways for Organic Synthesis","authors":"Helena Pletsch,Kilaparthi Sravan Kumar,Dominik P. Halter","doi":"10.1039/d6dt01709f","DOIUrl":"https://doi.org/10.1039/d6dt01709f","url":null,"abstract":"Oxygen atom transfer reactions (OAT) are a key transformation for the synthesis of commodity and fine chemicals, with existing processes relying on stoichiometric oxidants and sometimes harsh reaction conditions. Electrifying these reactions (e-OAT) to run at room temperature and to replace chemical oxidants with cheap electricity and the sustainable O-atom donors water or O2 can reduce environmental impact. At the same time, conceptually separating thermodynamic driving force provided via electricity from the identity of the oxygen atom source holds potential for unique selectivity that cannot easily be achieved with chemical oxidants. In order to spark new developments in the field of e-OAT, this perspective summarizes fundamental mechanistic aspects and successful examples of chemical OAT, to highlight connections as well as development potential of e-OAT reactions across epoxidation, C–H hydroxylation, sulfoxidation, N-oxidation and phosphine oxidation. Covering both, homogeneous and heterogeneous catalysts, the state of the art and most recent developments of these e-OAT reactions are included. We elaborate on the role of different reactive intermediates types and design principles for catalysts and reaction conditions, outlining how to achieve high reaction selectivity for e-OAT processes over parasitic side reactions such as O2 evolution, as well as strategies for challenging reactions such as partial methane oxidation to methanol. To inspire innovation, we visualize an overlap between active intermediates of e-OAT with OER and ORR catalysis platforms, with opportunity for repurposing existing successful catalysts for e-OAT. Finally, we showcase with selected examples that the successful application of e-OAT catalysis will eventually require a combined control over catalyst species as well as reactor design in essential combination, to reach demanding target reactions, such as epoxidation, methane hydroxylation or oxidative N2 fixation at full performance.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"3 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149152691","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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

Neodymium speciation in Cl-bearing aqueous solutions at 25–200 °C from Raman spectroscopy 25-200°C含cl水溶液中钕形态的拉曼光谱

IF 4 3区化学

Dalton Transactions Pub Date : 2026-10-13 DOI: 10.1039/d6dt01160h

Sarah E. Smith-Schmitz,Nicole C. Hurtig,Alexander P. Gysi,Laura E. Waters

{"title":"Neodymium speciation in Cl-bearing aqueous solutions at 25–200 °C from Raman spectroscopy","authors":"Sarah E. Smith-Schmitz,Nicole C. Hurtig,Alexander P. Gysi,Laura E. Waters","doi":"10.1039/d6dt01160h","DOIUrl":"https://doi.org/10.1039/d6dt01160h","url":null,"abstract":"Rare earth elements (REE) are strategic resources due to their uses in high-tech and energy efficient devices. The speciation of REE with ligands such as Cl− is important for REE transport in hydrothermal fluids and controls their mobility in ore deposits. Previous studies indicate that REE are mobilized in saline ore-forming fluids at >100–400 °C. Thermodynamic data for REE chloride complexes are largely based on solubility experiments, whereas most in situ Raman studies have been undertaken at ambient temperature. In this study, in situ Raman spectroscopy was used to measure the speciation of Nd in acidic solutions with variable chlorinity in fused quartz capillary cells from 25 to 200 °C. Raman bands specific to Nd–O and Nd–Cl bonds were identified near 350 cm−1 and 230 cm−1 respectively. Measurement of the Nd–O band in a Nd2O3–HClO4 solution was used to derive a scattering coefficient of 4.8 ± 0.3 × 10−3 for the Nd–O vibrational mode of the fully hydrated Nd3+ aqua ion. The logarithm of the species formation constant for NdCl2+ at zero ionic strength was determined to be 0.64 ± 0.03 at 25 °C and 1 bar, in good agreement with literature values derived using other indirect experimental methods. The log β1 and log β2 values derived at 100 to 200 °C also display generally good reproducibility with other experimental studies, indicating that Raman spectroscopy can be an accurate method for deriving thermodynamic constants for REE in hydrothermal solutions.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"32 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149152700","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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