结构化学最新文献

{"title":"Manipulate zirconium metal-organic frameworks in the ultramicroporous realm","authors":"Jingjing Zhang , Ji Guo , Wei Gong","doi":"10.1016/j.cjsc.2025.100658","DOIUrl":"10.1016/j.cjsc.2025.100658","url":null,"abstract":"","PeriodicalId":10151,"journal":{"name":"结构化学","volume":"44 9","pages":"Article 100658"},"PeriodicalIF":10.3,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145289735","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Tandem assembly-disassembly-reassembly of hierarchical Co19 coordination cluster facilitated by in-situ ligand transformation: Crystallography and ESI-MS revealed mechanism","authors":"Qiu-Jie Chen ,&nbsp;Tian-Ying Gu ,&nbsp;Zhao-Bo Hu ,&nbsp;Man-Bo Zhang ,&nbsp;Zheng Yin ,&nbsp;Ming-Hua Zeng","doi":"10.1016/j.cjsc.2025.100659","DOIUrl":"10.1016/j.cjsc.2025.100659","url":null,"abstract":"<div><div>Odd-numbered and high-nuclearity coordination clusters are extremely rare, yet they represent an intriguing subclass lacking regular repeating building blocks and high structural symmetry for understanding self-assembled multiatomic systems. Herein, the largest cobalt and polydentate ligand based cluster featuring odd-nuclearity, namely [Co₁₉(HL1)₈(L1)₁₂(L′)₂(Ac)₄]·10CH₃CH₂OH·6H₂O (<strong>1</strong>, H₂L1 = 1H-benzo[d]imidazole-2-yl)methanol, HL' = 1H-benzo[d]imidazole), was obtained with <em>in-situ</em> ligand transformation from H₂L1 to L′. It features a hierarchical trilayer and void-cage inside structure, consisting of central disc-shaped [Co₇L₁₀] core with two [Co₆] rings on both sides. ESI-MS of crystal <strong>1</strong> yields a series of more than sixteen fragments, all featuring an integrated [Co₁₉] core, suggesting stability of the polynuclear cluster in solution. During increased in-source energy from 0 to 100 eV, all MS peaks shifted to a lower <em>m</em>/<em>z</em> range, but the [Co₁₉] core remained intact, excepting for the stepwise elimination of up to three Ac⁻ anions or three L1 linkers. PXRD tracking of the reaction sediments showed the formation of a key precursor of [Co₄L₄] cubane at 3 h, and its content decreased at 6 h and vanished at 12 h, followed by the appearance of crystals <strong>1</strong> by the generation of a clear solution at 18 h, suggesting an initial cluster assembly-disassembly process. ESI-MS spectra analysis of both reaction sediment and solution further identify the existence of other crucial higher-nuclearity reassembled fragments of [Co₇L₁₀] disk and its expansion of [Co₁₃L₁₂(L′)₂]. A probable tandem assembly-disassembly-reassembly mechanism is put forward as [CoL₂]→[Co₄L₄]→[Co₇L₁₀]→[Co₁₃L₁₂(L′)₂]→[Co₁₉L₂₀(L′)₂]. Their evolution also indicated the ingenious synergy of coexisting organic, inorganic and <em>in-situ</em> generated ligands, along with diverse coordination geometries of metal ions, plays a directional role in forming odd-numbered and high-nuclearity coordination clusters. Magnetism analysis revealed antiferromagnetic coupling plays dominated role in the cluster.</div></div>","PeriodicalId":10151,"journal":{"name":"结构化学","volume":"44 9","pages":"Article 100659"},"PeriodicalIF":10.3,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145289742","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Periodic Janus structure based on ionic covalent organic framework for selective removal of perfluoroalkyl substances","authors":"Xiaojuan Sun ,&nbsp;Ke Kong ,&nbsp;Jun Liang ,&nbsp;Dan Wang ,&nbsp;Beibei Dong ,&nbsp;Ruihu Wang","doi":"10.1016/j.cjsc.2025.100652","DOIUrl":"10.1016/j.cjsc.2025.100652","url":null,"abstract":"<div><div><span><span>Per- and polyfluoroalkyl substances (PFAS) are persistent environmental contaminants<span> that often show an adverse impact on human health. Rational design of porous adsorbents for selective and reversible removal of PFAS, such as perfluorooctane </span></span>sulfonate<span> (PFOS), is imperative and challenging. Herein, a Janus strategy based on an ionic covalent organic framework (iCOF-DG</span></span>_Cl<span>) composed of the alternately hydrophobic aromatic domains and hydrophilic<span> guanidinium moieites has been proposed to meet the requirement of high-performance adsorbents. iCOF-DG</span></span>_Cl<span> shows fast adsorption kinetics (970.9 mg g</span>⁻¹ min⁻¹) and ultrahigh uptake capacity (2491 mg g⁻¹) toward PFOS, making it one of the most effective materials among the reported PFOS adsorbents. Moreover, the PFOS removal by iCOF-DG_Cl remains highly selective in the presence of disturbing anions, and the adsorbent could be well recovered for reuse. Mechanism studies have demonstrated that the Janus structure units of iCOF-DG_Cl<span> form both hydrophobic and electrostatic interactions<span> with the amphiphilic PFOS, thus achieving cooperative adsorption of PFOS. This work provides a facile approach based on Janus structure of COFs adsorbent for wastewater remediation.</span></span></div></div>","PeriodicalId":10151,"journal":{"name":"结构化学","volume":"44 9","pages":"Article 100652"},"PeriodicalIF":10.3,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145289737","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Preparation and characterization of metal carbenes M2C3− (M = Os, Ir, Pt)","authors":"Jianpeng Yang ,&nbsp;Ziheng Zhang ,&nbsp;Gang Li ,&nbsp;Juntao Cao ,&nbsp;Qiangshan Jing ,&nbsp;Hua Xie ,&nbsp;Ling Jiang","doi":"10.1016/j.cjsc.2025.100657","DOIUrl":"10.1016/j.cjsc.2025.100657","url":null,"abstract":"","PeriodicalId":10151,"journal":{"name":"结构化学","volume":"44 9","pages":"Article 100657"},"PeriodicalIF":10.3,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145290082","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Innovative optothermal-stimulated persistent luminescence nanoparticles for advanced tumor theranostics","authors":"Yuqing Zhang ,&nbsp;Xiao Song ,&nbsp;Yongsheng Liu ,&nbsp;Maochun Hong","doi":"10.1016/j.cjsc.2025.100624","DOIUrl":"10.1016/j.cjsc.2025.100624","url":null,"abstract":"","PeriodicalId":10151,"journal":{"name":"结构化学","volume":"44 7","pages":"Article 100624"},"PeriodicalIF":10.3,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144722281","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Crystal orientation dependent charge transfer dynamics and interfacial water configuration boosting photoelectrocatalytic water oxidation to H2O2","authors":"Yan Zhao ,&nbsp;Zhenming Tian ,&nbsp;Qisen Jia ,&nbsp;Ting Yao ,&nbsp;Jiashu Li ,&nbsp;Yanan Wang ,&nbsp;Xuejing Cui ,&nbsp;Jing Liu ,&nbsp;Xin Chen ,&nbsp;Luhua Jiang","doi":"10.1016/j.cjsc.2025.100619","DOIUrl":"10.1016/j.cjsc.2025.100619","url":null,"abstract":"<div><div>Photoelectrochemical water oxidation reaction (PEC-WOR) as a sustainable route to produce H₂O₂ is attractive but limited by low activity and poor product selectivity of photoanodes due to limited photogenerated charge efficiency and unfavorable thermodynamics. Herein, by crystal orientation engineering, the WO₃ photoanode exposing (200) facets achieves both superior WOR activity (15.4 mA cm⁻² at 1.76 V_RHE) and high selectivity to H₂O₂ (∼70%). Comprehensive experimental and theoretical investigations discover that the high PEC-WOR activity of WO₃-(200) is attributed to the rapid photogenerated charge separation/transfer both in bulk and at interfaces of WO₃-(200) facet, which reduces the charge transfer resistance. This, coupling with the unique defective hydrogen bonding network at the WO₃-(200)/electrolyte interface evidenced by <em>operando</em> PEC Fourier transform infrared spectroscopy, facilitating the outward-transfer of the WOR-produced H⁺, lowers the overall reaction barrier for the PEC-WOR. The superior selectivity of PEC-WOR to H₂O₂ is ascribed to the unique defective hydrogen bonding network alleviated adsorption of ∗OH over the WO₃-(200) facet, which specially lowers the energy barrier of the 2-electron pathway, as compared to the 4-electron pathway. This work addresses the significant role of crystal orientation engineering on photoelectrocatalytic activity and selectivity, and sheds lights on the underlying PEC mechanism by understanding the water adsorption behaviors under illumination. The knowledge gained is expected to be extended to other photoeletrochemical reactions.</div></div>","PeriodicalId":10151,"journal":{"name":"结构化学","volume":"44 7","pages":"Article 100619"},"PeriodicalIF":10.3,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144724111","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synthesis, separation and structure of zinc coordination clusters: Proposal of an assembly-disassembly-reassembly process observed from ESI-MS","authors":"Huang-Ling Lin ,&nbsp;Meng-Zhen Xu ,&nbsp;Tian-Ying Gu ,&nbsp;Xing-Xing Shi ,&nbsp;Mao Le,&nbsp;Zheng Yin,&nbsp;Ming-Hua Zeng","doi":"10.1016/j.cjsc.2025.100602","DOIUrl":"10.1016/j.cjsc.2025.100602","url":null,"abstract":"<div><div>In mass spectrometry, fragments with a mass higher than the original molecular ion provide valuable insights into the molecular structure and can guide the assembly and disassembly processes for chemical synthesis. Here, we report such an example and following up by modifying the solvothermal reaction conditions (temperature and time) it is possible to isolate the high mass species in crystalline form. [Zn₄L₄Cl₄] (<strong>Zn₄L₄</strong>, L = N-methylbenzimidazole-2-methanolate) has a boat-like Zn₄O₄ core but electrospray ionization mass spectrometry (ESI-MS) of the solution of its crystals shows higher mass peaks of Zn₅L₅, Zn₅L₆ and Zn₆L₆ species. Thus, both disassembly and reassembly are highly probable processes. Consequently, [Zn(HL)₂Cl₂] (<strong>Zn₁</strong>, L = N-methylbenzimidazole-2-methanolate), [Zn₄L₆Cl₂] (<strong>Zn₄L₆</strong>, L = N-methylbenzimidazole-2-methanolate) and [Zn₆L₆Cl₄(CH₃O)₂] (<strong>Zn₆L₆</strong>, L = N-methylbenzimidazole-2-methanolate) were prepared. The results of multistage ESI-MS of their dissolved crystals led to a proposed mechanism of their formation in the gas phase as follows: [Zn₃L₄] through [ZnL] → [ZnL(HL)] → [Zn(HL)₂] → [Zn₂L] → [Zn₂L₂] → [Zn₂L₃]. The mechanism was derived in conjunction with Gibbs free energies calculated using DFT of the fragments observed in the ESI-MS of <strong>Zn₄L₄</strong>, <strong>Zn₄L₆</strong> and <strong>Zn₆L₆</strong>. This work reveals the complex of chemical reactions, involving fragmentation and unexpected combination, under mass spectrometry condition which allows one to synthesize the observed transients, leading to mechanism of formation by correlation of solid-state/solution structural information.</div></div>","PeriodicalId":10151,"journal":{"name":"结构化学","volume":"44 7","pages":"Article 100602"},"PeriodicalIF":10.3,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144724109","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Type-I heterojunction photocatalysis: Enhanced activity via ZnIn2S4/MnCo2O4.5 interfacial electric fields","authors":"Qiang Yu ,&nbsp;Shuhan Sun ,&nbsp;Xianming Jin ,&nbsp;Ruiqiang Yan ,&nbsp;Bingjing He ,&nbsp;Nikolay Sirotkin ,&nbsp;Alexander Agafonov ,&nbsp;Xianqiang Xiong ,&nbsp;Kangle Lv","doi":"10.1016/j.cjsc.2025.100620","DOIUrl":"10.1016/j.cjsc.2025.100620","url":null,"abstract":"<div><div>The modulation of charge transfer pathways within type-I heterojunctions through interfacial electric field (IEF) engineering is of critical importance in promoting photocatalytic hydrogen evolution, effectively facilitating the separation of photogenerated charge carriers. In this study, we performed <em>in-situ</em> growth of two-dimensional ZnIn₂S₄ nanosheets on MnCo₂O_4.5 nanorods to construct an ohmic-like type-I ZnIn₂S₄/MnCo₂O_4.5 heterojunction for efficient photocatalytic hydrogen evolution. This ohmic-like charge transfer mechanism effectively addresses the intrinsic limitations inherent to conventional type-I heterojunctions neglecting IEF effects, particularly through IEF-induced enhancement of charge separation efficiency. Consequently, the optimized ZnIn₂S₄/MnCo₂O_4.5 photocatalyst demonstrates an outstanding photocatalytic hydrogen evolution rate of 20.9 mmol g⁻¹ h⁻¹, 14.9 times that of the bare ZnIn₂S₄. Furthermore, the ohmic-like charge transport behavior has been rigorously validated by integrated advanced experimental characterizations, including <em>in-situ</em> X-ray photoelectron spectroscopy (XPS), Kelvin probe force microscopy (KPFM), and surface photovoltage (SPV) measurements, which collectively provide robust evidence for the proposed mechanism. This work offers valuable insights into the design of high-efficient ohmic-like type-I heterojunction catalysts for photocatalytic H₂ evolution.</div></div>","PeriodicalId":10151,"journal":{"name":"结构化学","volume":"44 7","pages":"Article 100620"},"PeriodicalIF":10.3,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144724112","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Four tartaric acid-bridged tetra-europium(III)-containing antimonotungstate with catalytic oxidation of thioethers/alcohols","authors":"Yuanping Jiang ,&nbsp;Haoqi Liu ,&nbsp;Jiawei Zhang ,&nbsp;Luying Jiao,&nbsp;Xiaoling Lin,&nbsp;Fuhua Zhang,&nbsp;Guoping Yang","doi":"10.1016/j.cjsc.2025.100603","DOIUrl":"10.1016/j.cjsc.2025.100603","url":null,"abstract":"<div><div>A novel tetra-europium(III)-containing antimonotungstate, Na_8.2[H₂N(CH₃)₂]₉[Na_10.8(tar)₄(H₂O)₂₀(Eu₂Sb₂W₂₁O₇₂)₂]·44.5H₂O (<strong>EuSbW</strong>, H₄tar = <span>dl</span>-tartaric acid), has been synthesized and characterized. The dimeric polyoxoanion of <strong>EuSbW</strong> consists of two Dawson-like {Eu₂Sb₂W₂₁} units bridged by four <span>dl</span>-tartaric acid ligands. The adjacent carboxyl and hydroxy groups in each tartaric acid simultaneously chelate with W and Eu atoms from different {Eu₂Sb₂W₂₁} units, thereby forming the dimeric structure. <strong>EuSbW</strong> represents an extremely rare polyoxometalate where four tartaric acid ligands function as connectors to bridge two {Eu₂Sb₂W₂₁} units. Additionally, <strong>EuSbW</strong> exhibits excellent catalytic activity and reusability in the oxidation of thioethers and alcohols, achieving 100% conversion and &gt; 99% selectivity for various thioethers, and 85–100% conversion with 90–99% selectivity for diverse alcohols under mild conditions.</div></div>","PeriodicalId":10151,"journal":{"name":"结构化学","volume":"44 7","pages":"Article 100603"},"PeriodicalIF":10.3,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144722279","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Photomechanical movements of a coordination polymer-based composite enable a reversible photocontrollable electrical switch","authors":"Qian Ren ,&nbsp;Shu-Fen Zhang ,&nbsp;Dong Liu ,&nbsp;Jian-Ping Lang","doi":"10.1016/j.cjsc.2025.100622","DOIUrl":"10.1016/j.cjsc.2025.100622","url":null,"abstract":"<div><div>Flexible circuit switches have been widely used in electronic devices due to their outstanding flexibility and operability. In order to expand the types of flexible circuit switch materials, we develop a unique composite material, which integrates a photoresponsive flexible substrate derived from a photoreactive coordination polymer (CP) with an elastic conductive adhesive tape (CAT) in this work. The photoreactive CP {[Cd(2,6-bpvn)(3,5-DBB)₂]·DMF}_<em>n</em> (<strong>1</strong>) is prepared through solvothermal reaction of Cd(NO₃)₂·4H₂O with 2,6-bis((<em>E</em>)-2-(pyridin-4-yl)vinyl)naphthalene (2,6-bpvn) and 3,5-dibromobenzoic acid (3,5-HDBB). Upon irradiation with UV light, crystals of <strong>1</strong> can undergo [2 + 2] photocycloaddition reaction and exhibit photomechanical movements. The crystalline powder of <strong>1</strong> can be uniformly distributed in polyvinyl alcohol (PVA) to generate the composite film <strong>1-PVA</strong>. After pasting a piece of CAT on the surface of a <strong>1-PVA</strong> film, a conductive two-layer film of <strong>1-PVA/CAT</strong> can be fabricated. This film bends rapidly upon UV light exposure, connecting the circuit and causing the bulb to light up. When the light source is removed, it reverts to its initial state and the circuit is disconnected and the bulb is extinguished. This process can be cycled at least 100 times, achieving precise turn-on and turn-off performances of the photocontrollable circuit switch.</div></div>","PeriodicalId":10151,"journal":{"name":"结构化学","volume":"44 7","pages":"Article 100622"},"PeriodicalIF":10.3,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144724114","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}