Dalton Transactions最新文献

{"title":"Intercalation of alkali metal into WTe2, the crystal structure of A0.5WTe2 and observation of a metal-to-semiconductor transition","authors":"Patrick Schmidt, Fabian Strauß, Marcus Scheele, Carl P. Romao, Hans-Jürgen Meyer","doi":"10.1039/d5dt02775f","DOIUrl":"https://doi.org/10.1039/d5dt02775f","url":null,"abstract":"We explore the cationic intercalation of tungsten ditelluride (WTe<small>₂</small>) with potassium (K), rubidium (Rb), and cesium (Cs), yielding intercalation compounds of the form <em>A</em><small>_0.5</small>WTe<small>₂</small> (<em>A</em> = K, Rb, Cs). Structural characterization was performed using powder X-ray diffraction (PXRD), while diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy and temperature-dependent conductivity measurements were employed to investigate the electronic properties. Density functional theory (DFT) calculations were carried out to support the experimental findings and to provide insight into the intercalation mechanisms and the resulting material characteristics. All synthesized compounds display semiconducting behavior with narrow band gaps, emphasizing the influence of alkali metal intercalation on the electronic structure and transport properties of WTe<small>₂</small>. These results advance the fundamental understanding of property modulation in transition-metal dichalcogenides (TMDCs) and highlight their potential for electronic device applications.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"19 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116151","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}

{"title":"[Ru6(μ6-Sb)(CO)18]3-: Deeply Reduced Metal Carbonyl Cluster Embedded with Naked μ6-Sb","authors":"Cheng Ding, Xian Xu, qian qin, Jingen Ding, Li Xu","doi":"10.1039/d6dt00002a","DOIUrl":"https://doi.org/10.1039/d6dt00002a","url":null,"abstract":"The redox reaction of K3Sb and Ru3(CO)12 in the ethylenediamine (en) of 2,2,2-cryptand to produce the deeply reduced [Ru6(μ6-Sb)(μ2-CO)2(CO)16]3- (1) wherein the unprecedented boat-like Ru6 cluster unit is embedded with μ6-Sb for the first time. Structural and bonding evolution from the reported electroneutral {Ru6(μ5-Sb)(μ2-H)3(CO)18SbPh3} (2) to the negatively charged 1 have been discussed.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"17 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116144","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}

{"title":"NIR-Responsive Upconversion Nanoplatforms: an Anionic Drug Carrier for ROS Amplification Induced by β-amyloid Fibrils","authors":"Xiaofeng Jia, Yijia Guan, Weijie Cao, Xiaoshuo Zhang, Huazhen Duan, Hui Guo, Huichang Chen, Binbin Wang, Tao Li, Jianguo Liao","doi":"10.1039/d5dt03121d","DOIUrl":"https://doi.org/10.1039/d5dt03121d","url":null,"abstract":"Alzheimer’s disease (AD), marked by the misfolding/aggregation of β-amyloid (Aβ), is a major global health challenge. Polyoxometalates (POMs), as anionic therapeutic agents, exhibit potential in depolymerizing Aβ fibrils, inhibiting Aβ fibrillation, and photocatalyst. To achieve targeted reactive oxygen species (ROS) amplification, we developed a chitosan-modified near-infrared (NIR)-responsive upconversion nanoplatform, UCNPs(Tm/Er)@SiO2@GPS@CH, as a targeted carrier for POMs. The nanoplatform was constructed by sequentially modifying upconversion nanoparticles (UCNPs) with a silica layer, 3-glycidoxypropyltrimethoxysilane (GPS, as a linker), and chitosan (CH, a cationic biomacromolecule). The cationic CH layer enabled efficient loading of anionic POMs through electrostatic interactions with an optimal POMs loading capacity of 415.41 μg/mg that positively correlated with CH modification levels. Under NIR irradiation, the nanoplatform triggered a photodynamic effect with abundant ROS. Notably, compared with the control group and Aβ monomer group, the ROS generation in the Aβ fibril group was approximately doubled, which further enhanced the targeted therapeutic efficacy of system. By integrating NIR responsiveness, cationic chitosan, targeted ROS generation, and low systemic toxicity, the nanoplatform provides a novel strategy for the photooxidative treatment of AD and offers insights into the design of chitosan-modified upconversion nanoparticles-based drug carrier systems.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"1 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116128","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}

{"title":"Synthesis, structural characterization and properties of a series of heteropolyoxomolybdates: [AlMo6(OH)6O18]3−, [GeMo12O40]4−, [GeMo6O22(Hmal)3]7−, [SiMo12O40]4−, and [TeMo6O24]6−","authors":"D. Kuzman, V. Damjanović, J. Toplak, G. Medak, I. Halasz, T. Hrenar, M. Cindrić, V. Vrdoljak","doi":"10.1039/d5dt03064a","DOIUrl":"https://doi.org/10.1039/d5dt03064a","url":null,"abstract":"Eight heteropolyoxomolybdates were synthesized and characterized, comprising three Anderson-type compounds [Co(ox)(NH&lt;small&gt;&lt;sub&gt;3&lt;/sub&gt;&lt;/small&gt;)&lt;small&gt;&lt;sub&gt;4&lt;/sub&gt;&lt;/small&gt;]&lt;small&gt;&lt;sub&gt;3&lt;/sub&gt;&lt;/small&gt;[AlMo&lt;small&gt;&lt;sub&gt;6&lt;/sub&gt;&lt;/small&gt;(OH)&lt;small&gt;&lt;sub&gt;6&lt;/sub&gt;&lt;/small&gt;O&lt;small&gt;&lt;sub&gt;18&lt;/sub&gt;&lt;/small&gt;]·7H&lt;small&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/small&gt;O (&lt;strong&gt;1&lt;/strong&gt;), [Co(ox)(NH&lt;small&gt;&lt;sub&gt;3&lt;/sub&gt;&lt;/small&gt;)&lt;small&gt;&lt;sub&gt;4&lt;/sub&gt;&lt;/small&gt;]&lt;small&gt;&lt;sub&gt;6&lt;/sub&gt;&lt;/small&gt;[TeMo&lt;small&gt;&lt;sub&gt;6&lt;/sub&gt;&lt;/small&gt;O&lt;small&gt;&lt;sub&gt;24&lt;/sub&gt;&lt;/small&gt;]·16H&lt;small&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/small&gt;O (&lt;strong&gt;2&lt;/strong&gt;), and Na&lt;small&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/small&gt;[Co(ox)(en)&lt;small&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/small&gt;]&lt;small&gt;&lt;sub&gt;4&lt;/sub&gt;&lt;/small&gt;[TeMo&lt;small&gt;&lt;sub&gt;6&lt;/sub&gt;&lt;/small&gt;O&lt;small&gt;&lt;sub&gt;24&lt;/sub&gt;&lt;/small&gt;]·16H&lt;small&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/small&gt;O (&lt;strong&gt;3&lt;/strong&gt;), four Keggin-type compounds [Co(ox)(NH&lt;small&gt;&lt;sub&gt;3&lt;/sub&gt;&lt;/small&gt;)&lt;small&gt;&lt;sub&gt;4&lt;/sub&gt;&lt;/small&gt;]&lt;small&gt;&lt;sub&gt;4&lt;/sub&gt;&lt;/small&gt;[GeMo&lt;small&gt;&lt;sub&gt;12&lt;/sub&gt;&lt;/small&gt;O&lt;small&gt;&lt;sub&gt;40&lt;/sub&gt;&lt;/small&gt;]·6H&lt;small&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/small&gt;O (&lt;strong&gt;4&lt;/strong&gt;), [Co(ox)(NH&lt;small&gt;&lt;sub&gt;3&lt;/sub&gt;&lt;/small&gt;)&lt;small&gt;&lt;sub&gt;4&lt;/sub&gt;&lt;/small&gt;]&lt;small&gt;&lt;sub&gt;4&lt;/sub&gt;&lt;/small&gt;[SiMo&lt;small&gt;&lt;sub&gt;12&lt;/sub&gt;&lt;/small&gt;O&lt;small&gt;&lt;sub&gt;40&lt;/sub&gt;&lt;/small&gt;]·6H&lt;small&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/small&gt;O (&lt;strong&gt;5&lt;/strong&gt;), [Co(ox)(en)&lt;small&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/small&gt;]&lt;small&gt;&lt;sub&gt;4&lt;/sub&gt;&lt;/small&gt;[GeMo&lt;small&gt;&lt;sub&gt;12&lt;/sub&gt;&lt;/small&gt;O&lt;small&gt;&lt;sub&gt;40&lt;/sub&gt;&lt;/small&gt;]·12H&lt;small&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/small&gt;O (&lt;strong&gt;6&lt;/strong&gt;), and [Co(ox)(en)&lt;small&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/small&gt;]&lt;small&gt;&lt;sub&gt;4&lt;/sub&gt;&lt;/small&gt;[SiMo&lt;small&gt;&lt;sub&gt;12&lt;/sub&gt;&lt;/small&gt;O&lt;small&gt;&lt;sub&gt;40&lt;/sub&gt;&lt;/small&gt;]·12H&lt;small&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/small&gt;O (&lt;strong&gt;7&lt;/strong&gt;), as well as one coordination polymer Na&lt;small&gt;&lt;sub&gt;4&lt;/sub&gt;&lt;/small&gt;[Co(ox)(NH&lt;small&gt;&lt;sub&gt;3&lt;/sub&gt;&lt;/small&gt;)&lt;small&gt;&lt;sub&gt;4&lt;/sub&gt;&lt;/small&gt;]&lt;small&gt;&lt;sub&gt;3&lt;/sub&gt;&lt;/small&gt;[GeMo&lt;small&gt;&lt;sub&gt;6&lt;/sub&gt;&lt;/small&gt;O&lt;small&gt;&lt;sub&gt;22&lt;/sub&gt;&lt;/small&gt;(Hmal)&lt;small&gt;&lt;sub&gt;3&lt;/sub&gt;&lt;/small&gt;]·7.75H&lt;small&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/small&gt;O (&lt;strong&gt;8&lt;/strong&gt;) featuring an extensive three-dimensional coordination framework. Additionally, two reaction intermediates, [{Co(ox)(NH&lt;small&gt;&lt;sub&gt;3&lt;/sub&gt;&lt;/small&gt;)&lt;small&gt;&lt;sub&gt;4&lt;/sub&gt;&lt;/small&gt;}&lt;small&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/small&gt;Na&lt;small&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/small&gt;(H&lt;small&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/small&gt;O)&lt;small&gt;&lt;sub&gt;6&lt;/sub&gt;&lt;/small&gt;{H&lt;small&gt;&lt;sub&gt;4&lt;/sub&gt;&lt;/small&gt;Mo&lt;small&gt;&lt;sub&gt;8&lt;/sub&gt;&lt;/small&gt;O&lt;small&gt;&lt;sub&gt;28&lt;/sub&gt;&lt;/small&gt;}]·4H&lt;small&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/small&gt;O (&lt;strong&gt;1a&lt;/strong&gt;) and [Co(ox)(NH&lt;small&gt;&lt;sub&gt;3&lt;/sub&gt;&lt;/small&gt;)&lt;small&gt;&lt;sub&gt;4&lt;/sub&gt;&lt;/small&gt;]&lt;small&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/small&gt;[Al(mal)&lt;small&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/small&gt;(H&lt;small&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/small&gt;O)&lt;small&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/small&gt;]·Hmal·2H&lt;small&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/small&gt;O (&lt;strong&gt;1b&lt;/strong&gt;), were also isolated. Compounds [Co(NH&lt;small&gt;&lt;sub&gt;3&lt;/sub&gt;&lt;/small&gt;)&lt;small&gt;&lt;sub&gt;6&lt;/sub&gt;&lt;/small&gt;][Al(mal)&lt;small&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/small&gt;(H&lt;small&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/small&gt;O)&lt;small&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/small&gt;](NO&lt;small&gt;&lt;sub&gt;3&lt;/sub&gt;&lt;/small&gt;)&lt;small&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/small&gt;·H&lt;small&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/small&gt;O (&lt;strong&gt;9&lt;/strong&gt;) and [Co(en)&lt;small&gt;&lt;sub&gt;3&lt;/sub&gt;&lt;/small&gt;]&lt;small&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/small&gt;[Mo&lt;small&gt;&lt;sub&gt;8&lt;/sub&gt;&lt;/small&gt;O&lt;small&gt;&lt;sub&gt;26&lt;/sub&gt;&lt;/sm","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"46 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116061","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}

{"title":"Tuning the Morphology of ZnCdS@CeO2 Z-scheme Heterostructures From Core-Shell to Core-Satellite for Superior Photocatalytic Performance","authors":"Yong Liu, Baowei Shen, Sijia Zhao, Guixia Ma, Yujie Ma, Yu Xia, Xing Wang, Yuhua Feng","doi":"10.1039/d6dt00034g","DOIUrl":"https://doi.org/10.1039/d6dt00034g","url":null,"abstract":"In addition to solar cell, photocatalysis is an alternative way for the direct utilization of the clean and sustainable solar energy. Currently, the core challenge in photocatalysis is the efficiency of the separation and transfer of the photogenerated electrons (e⁻) and holes (h⁺) in photocatalysts. Herein, continuous tuning of ZnCdS-CeO2 heterostructures via a seed-mediated growth approach yielded two typical hybrid structures: ZnCdS-CeO2 core-satellite (ZCSC I) and ZnCdS@CeO2 core-shell (ZCSC II) structures. Leveraging the Janus configuration of ZCSC I structure, a marked improvement in charge separation and transfer efficiency was observed in photocurrent and transient fluorescence tests. This enhancement should be due to the electron “sink effect” in ZCSC I structure as the spatial separation of the ZnCdS (ZCS) and CeO2 domains. Furthermore, the photocatalytic activity of the heterostructures was evaluated using the photocatalytic degradation of methylene blue (MB) as a model reaction. Consistent with the above tests, the ZCSC I showed the highest MB degradation rate of 91% within 60 minutes. From the calculated kinetic rate constants (k values), the k value of ZCSC I structure is 4, 2.1, and 1.5 times higher than those of CeO2, ZCS, and ZCSC II structure, respectively. Through radical trapping experiments, the ZnCdS-CeO2 heterostructures were identified as Z-scheme heterojunction. This work provides solid mechanistic understanding and valuable insights for improving the catalytic efficiency of hybrid photocatalysts, which is helpful for the rational design and precise control of the hybrid photocatalysts with high catalytic efficiency and would assist their applications in diverse catalytic reactions.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"223 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122351","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}

{"title":"Synthesis, structures and catalytic properties of two organic-inorganic hybrid polyoxometalates built from {Ni6PW9} units","authors":"Shuang Gao, Zhen-Wen Wang, Guo-Yu Yang","doi":"10.1039/d5dt03040d","DOIUrl":"https://doi.org/10.1039/d5dt03040d","url":null,"abstract":"Two new Ni6-added organic-inorganic hybrid polyoxometalates, {[Ni(en)2][Ni6(μ3-OH)3(H2O)3(Hen)(en)3(3,5-DDB)(B-α-PW9O34)][Ni6(μ3-OH)3(H2O)2(en)3(Ac)(3,5-DDB)(B-α-PW9O34)]}·8H2O (1, en = ethylenediamine, 3,5-DDB = 3,5-Dihydroxybenzoic acid) and [Ni(en)2][Ni6(μ3-OH)3(H2O)4(en)2(5-HIP)(B-α-PW9O34)]·3H2O (2, 5-HIP = 5-Hydroxyisophthalic acid) were synthesized by lacunary directing synthetic strategy. 1 forms a novel dumbbell-shaped dimer structure, consisting of two distinct Ni6-added POMs linked by [Ni(en)2]2+ cations. 2 exhibits one-dimensional (1D) chain structure assembled from [Ni6(μ3-OH)3(H2O)4(en)2(B-α-PW9O34)]2– structural building units bridged by 5-HIP ligands. Electrochemical studies revealed that 1 exhibits significant electrocatalytic activity for the reduction of H2O2 and NO2⁻. Furthermore, evaluation experiments on oxidative desulfurization revealed that complex 2 exhibited a higher desulfurization conversion rate for dibenzothiophene (DBT) compared to complex 1. Additionally, it was observed that increasing both the reaction temperature and the amount of H2O2 further improved the desulfurization efficiency of DBT.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"301 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116147","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}

{"title":"Potassium Follows Calcium in Heterobimetallic 'K-H-Al' Hydrides on a Picolyl-Derived Chemically Non-innocent Triaza Ligand","authors":"Chhotan Mandal, Abhishek Kundu, Sourav Panda, Debabrata Mukherjee","doi":"10.1039/d6dt00079g","DOIUrl":"https://doi.org/10.1039/d6dt00079g","url":null,"abstract":"Heterobimetallic hydrides pairing s- and p-block metals on a single ligand are rare but likely promising for synergic chemistry. We report a series of K-H-Al heterobimetallic hydrides on a chemically non-innocent picolyl-based ethylenediamine ligand through a metal-ligand interplaying mechanism of hydride shuttling. The proligands Ar3NH (Ar = Mes, Ph) and AlH3(NMe2Et) give the AlH2 complexes [(Ar3N)AlH2] (Ar = Mes (1), Ph (6)). Both 1 and 6 react with KN(SiMe3)2 (KHMDS) at room temperature to form 1:1 adducts ‘[(Mes3N)Al(HMDS)(H)2K]’ (7) and [(Ph3N)Al(HMDS)(H)2K]2 (8), respectively. Heating 7 and 8 at 70 °C deprotonates a picolyl C-H to give [(Mes3N-H)Al(HMDS)(H)K]4 (9) and [(Ph3N-H)Al(HMDS)(H)K]2 (10), respectively. Monitoring the thermolysis of 7 to 9 at 50 °C reveals an intermediate [(Mes3N2H)Al(HMDS)(H)K]2 (11), where the ligand pyridyl is reduced by a 2-H insertion. DFT analysis suggests the inserted hydride moves onto the potassium before the deprotonation happens. The overall reaction profile follows a similar Ca-H-Al heterobimetallic case on the same ligand framework, except an adduct like 7 or 8 was unseen before. A Li-Al combination on the same framework differs from the K-Al or Ca-Al cases but follows the pattern of Mg-Al.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"145 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146101501","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}

{"title":"Cu-exchanged phosphomolybdic acid induced solvent effect to enhance alkene epoxidation with H2O2","authors":"Xiaojing Song, Shuang Liu, Jing Wang, Tingting Wu, Lina Liu, Hao Zhang","doi":"10.1039/d5dt02762d","DOIUrl":"https://doi.org/10.1039/d5dt02762d","url":null,"abstract":"Solvent-mediated alkenes epoxidation using H2O2 oxidant is significantly enhanced by a Cu-substituted phosphomolybdic acid anchored on triphenylamine-functionalized porous organic polymers (CuPMA/POPs). The immobilization of CuPMA cluster on POPs supported suppressed the stronger coordinative interactions between Cu ion and PMA cluster, and brings obvious solvent effect. In 1, 4-dioxane, CuPMA/POPs achieves 90% conversion of cyclooctene, and markedly improves epoxide selectivity in styrene oxidation (65.5% vs 36.9% for PMA/POPs). Based on various characterizations, phosphomolybdic acid did not form the active species [PO4MoO(O2)]3-, which typically arise from the interaction PMA-H2O2. Instead, the incorporation of Cu modulates the electronic structure of PMA, facilitating the generation of active peroxo intermediates such as Cu-OOH and Mo-OOH. These species promote oxygen-atom transfer to the C=C bond, thus benefiting for the high epoxides selectivity. Additionally, the hydrogen-bonding network from the solvent effect between by 1,4-dioxane and H2O2 further enhances the reaction efficiency. The catalyst also exhibits excellent recyclability due to strong host-guest interactions, underscoring the synergy between Cu substitution and solvent effects in promoting efficient and stable epoxidation catalysis.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"111 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116149","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}

{"title":"Blue-Light-Driven Aerobic Oxidation via Superoxide Radical-Generating Zinc(II)-Organic Framework Photocatalyst","authors":"Jing Zhu, Yumeng Zhang, Juanle Zhang, Junan Ma, Chang-Chun Liu, Xiaoxing Ma","doi":"10.1039/d5dt02529j","DOIUrl":"https://doi.org/10.1039/d5dt02529j","url":null,"abstract":"The development of sustainable and efficient photocatalytic systems for aerobic oxidation is a crucial challenge in the field of green chemistry. In this study, we present the rational design and synthesis of a novel zinc(II)-organic framework (Zn-1D) by incorporating anthracene-based photoactive ligands with zinc(II)-oxo clusters. Zn-1D demonstrates significant absorption in the blue-light region (&lt;450 nm), effective charge separation, and the ability to generate superoxide radicals (O2 •-).Structural analysis confirms a crystalline 1D chained structure with hierarchical porosity. Mechanistic investigations reveal a synergistic effect between anthracene-mediated light absorption and zinc(II)-mediated redox reactions. Under blue-light irradiation, Zn-1D exhibits outstanding catalytic performance in aerobic oxidation reactions, such as the thioether oxidation.The microporous channels of the framework stabilize reactive intermediates, preventing overoxidation. Moreover, its excellent chemical and thermal stability allow for five consecutive recycling cycles without loss of activity. This work provides a new model for noble-metal-free photocatalysis by utilizing MOF-confined dual-function sites for blue-light-driven organic transformations, thus promoting the development of sustainable synthetic methods.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"79 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146101500","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}

{"title":"Inter-Ligand Cross-Links Determine Secondary Building Unit Formation in OligoMOFs","authors":"Debobroto Sensharma, Victor Branco B de Sousa, Seth M Cohen","doi":"10.1039/d5dt03049h","DOIUrl":"https://doi.org/10.1039/d5dt03049h","url":null,"abstract":"OligoMOFs are a new class of metal-organic frameworks (MOFs) that feature ligands covalently cross-linked into oligomers as intrinsic structural components. Recent studies have demonstrated that the size and flexibility of the tether moieties can result in the formation of oligoMOFs with different isomeric structures via geometrical distortions in the secondary building unit (SBU). In this work, it is demonstrated that tethered dimeric ligands with slightly different carbon chain lengths can direct the formation of oligoMOFs with SBUs of different structure and nuclearity. Specifically, inter-ligand cross links are used as a sensitive probe of the phase landscape of MOFs with the composition [Zn2(R-bdc)2(bpy)] (bdc = 1,4benzenedicarboxylate, bpy = 4,4'-bipyridine), showing that a hexyl tether result in a framework structure identical to MOF-508, based on dinuclear {Zn2} \"paddlewheel\" SBUs, while heptyl and octyl tethers result in a \"honeycomb-like\" framework structure based on an infinite rod-like Zn 2+ SBU bridged by carboxylate ligands. These results are the first examples of tether length influencing SBU chemistry in MOFs and help understand the interplay between the MOF lattice and the geometric constraints imposed by inter-ligand cross-links in oligoMOFs.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"1 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146101503","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}