CrystEngComm最新文献

{"title":"Novel supramolecular structures constructed through hydrogen bonding (E–H⋯Cl; E = C, N, and O) and/or halogen–halogen interactions in the products of reactions of 2-[(trimethylsilyl)methyl]pyridine with TeCl4 or TeI4","authors":"Aarti Saini, Dharmveer Bhedi and Ramalingam Thirumoorthi","doi":"10.1039/D5CE00646E","DOIUrl":"https://doi.org/10.1039/D5CE00646E","url":null,"abstract":"<p >Three new complexes, [(2-C<small>₅</small>H<small>₄</small>NH)CH<small>₂</small>TeI<small>₄</small>] (<strong>1</strong>), [2-(Me<small>₃</small>SiCH<small>₂</small>)C<small>₅</small>H<small>₄</small>NH]<small>₂</small>[TeCl<small>₆</small>] (<strong>2</strong>), and [2-(CH<small>₃</small>)C<small>₅</small>H<small>₄</small>NH]<small>₂</small>[(HO)TeCl<small>₅</small>] (<strong>3</strong>), were obtained by the direct reaction of 2-[(trimethylsilyl)methyl]pyridine with TeI<small>₄</small> or TeCl<small>₄</small> in toluene. Single-crystal X-ray diffraction analysis (SCXRD) confirms that compound <strong>1</strong> is the first zwitterion-type complex in the organotellurium iodide family, whereas the remaining two are ionic. The asymmetric unit in <strong>2</strong> has only one-half of the anionic unit of [TeCl<small>₆</small>]<small>²⁻</small>, whereas a whole unit is present in <strong>3</strong>, because the latter anionic species loses 2<small>₁</small> screw axes. A discrete organotellurium iodide complex, [(2-C<small>₅</small>H<small>₄</small>NH)CH<small>₂</small>TeI<small>₄</small>], transforms into a dimer, [(2-C<small>₅</small>H<small>₄</small>NH)CH<small>₂</small>TeI<small>₄</small>]<small>₂</small>, due to weak secondary Te⋯I interactions, and subsequently, it transforms into a 2D-structure, [(2-C<small>₅</small>H<small>₄</small>NH)CH<small>₂</small>TeI<small>₄</small>]<small>_<em>n</em></small>, through iodine–iodine intermolecular interactions. The formation of 2D-supramolecular structures arises through intermolecular hydrogen bonding between a pyridinium cation and [TeCl<small>₆</small>]<small>²⁻</small> (<strong>2</strong>)/[(HO)TeCl<small>₅</small>]<small>²⁻</small> (<strong>3</strong>) anionic species. A weak chlorine–chlorine interaction is seen in both <strong>2</strong> and <strong>3</strong>.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 38","pages":" 6373-6380"},"PeriodicalIF":2.6,"publicationDate":"2025-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145183997","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":"Metal organic framework with high water stability and dense open metal sites for carbon monoxide capture","authors":"Yucong Xia, Julia Piper Radtke, Timo Thonhauser, Nathan M. Rabideaux and Jing Li","doi":"10.1039/D5CE00741K","DOIUrl":"https://doi.org/10.1039/D5CE00741K","url":null,"abstract":"<p >We report the synthesis, characterization and carbon monoxide (CO) adsorption properties of a series of isoreticular and water-stable metal–organic frameworks M<small>₂</small>Cl<small>₂</small>(bbta) (M = Co, Mn, Cu), composed of a one-dimensional (1D) metal-chloride chain building unit and a triazolate linker. Among them, Co<small>₂</small>Cl<small>₂</small>(bbta) exhibits the most promising performance for CO capture. Featuring a high density of open cobalt sites (3.8 nm<small>⁻³</small>), Co<small>₂</small>Cl<small>₂</small>(bbta) takes up 3.06 mmol g<small>⁻¹</small> of CO at 298 K, with a high isosteric heat of adsorption (<em>Q</em><small>_st</small>) of 35 kJ mol<small>⁻¹</small>, indicating strong interaction at the Co(<small>II</small>) centers. This interaction as a function of loading is further analyzed with the help of <em>ab initio</em> calculations. Remarkably, the framework maintains structural integrity and adsorption capacity after prolonged water exposure and multiple adsorption–desorption cycles. These results highlight Co<small>₂</small>Cl<small>₂</small>(bbta) as an example of a hydrolytically stable, OMS-rich MOF suitable for reversible CO capture. Its durability, regenerability, and strong affinity for CO make it a promising candidate for real-world gas separation and storage applications.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 38","pages":" 6381-6385"},"PeriodicalIF":2.6,"publicationDate":"2025-09-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ce/d5ce00741k?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145183998","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Mastering interfaces: advances and challenges in controlling protein nucleation","authors":"Fiora Artusio","doi":"10.1039/D5CE00767D","DOIUrl":"https://doi.org/10.1039/D5CE00767D","url":null,"abstract":"<p >Interfaces are ubiquitous in nature and are involved in any physico-chemical process. Crystallizing a protein implies the formation of a new interface between the growing crystalline material and the liquid solution. The nucleation step, which is pivotal to the formation of crystals, is extremely sensitive to the presence of interfaces. Such a feature can be exploited to aid the control of this delicate step, improving the chances of getting protein crystals, the reproducibility of the experiment, and the uniformity of the attributes of the crystals, <em>i.e.</em>, size, habit, and form. To do this, several approaches have been proposed in recent years, focusing on the use of controlled functionalization of surfaces and nanoparticles, the establishment of diffusion-dominated systems, and, more in general, the use of heteronucleants and additives. Recent advancements and current challenges in the field are here highlighted, including continuous protein crystallization and micro-crystallization.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 37","pages":" 6106-6121"},"PeriodicalIF":2.6,"publicationDate":"2025-09-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ce/d5ce00767d?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145100549","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Generalized chalcogenation for boosting the electrocatalytic alcohol oxidation of Pd nanoflowers","authors":"Zuoran Li, Lijie Zhu, Li Liu, Zhiwei He, JingYi Jiang, Hongyi Chen and Jiafu Zhong","doi":"10.1039/D5CE00688K","DOIUrl":"https://doi.org/10.1039/D5CE00688K","url":null,"abstract":"<p >The electrocatalytic alcohol oxidation reaction (AOR) is a crucial process in fuel cells; however, conventional electrocatalysts underperform owing to their limited electrocatalytic activity and poor stability, and achieving the dissociation of C–C bonds in alcohols is one of the biggest challenges in improving AOR efficiency. Herein, we propose a generalized chalcogenation strategy for significantly promoting the electrocatalytic AOR performance of Pd nanoflowers. Surprisingly, the mass activity and specific activity of the ethylene glycol oxidation reaction (EGOR) based on the optimized Pd<small>₈</small>Te<small>₁</small> nanocatalyst remarkably enhanced by 1.72 and 1.25 times, respectively. In addition to the EGOR, the as-obtained PdTe electrocatalysts were demonstrated to be highly active toward the ethanol oxidation reaction (EOR) and glycerol oxidation reaction (GOR). Detailed investigations reveal that their superior electrocatalytic activity and durability are attributed to the effect of chalcogenation, which could induce modification of the electronic structure of Pd to not only boost electron transfer but also significantly decrease the activation energy. More significantly, the chalcogenation strategy is general and thus can be extended to construct other efficient AOR electrocatalysts with enhanced performance. Considering the high electrocatalytic properties and facile synthesis method, we suggest that this generalized chalcogenation strategy will open a new avenue for the production of advanced electrocatalysts and boost the development of fuel cells.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 38","pages":" 6324-6332"},"PeriodicalIF":2.6,"publicationDate":"2025-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145183993","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":"Influence of thorium dioxide powder synthesis methods on conventional and spark plasma sintering†","authors":"Sorin-Octavian Vălu, Walter Bonani, Jacobus Boshoven, Karin Popa and Marco Cologna","doi":"10.1039/D5CE00459D","DOIUrl":"https://doi.org/10.1039/D5CE00459D","url":null,"abstract":"<p >We investigated the influence of the synthesis method on the properties of ThO<small>₂</small> powders and on their sinterability in conventional and spark plasma sintering (SPS). The powders were obtained by precipitation of thorium oxalate or thorium hydroxide, and further processed by low-temperature calcination at 600 °C or hydrothermal conversion at 250 °C. All powders had nanocrystallites &lt;10 nm and a high surface area, which allow the onset of sintering at reduced temperatures. However, the presence of larger voids and non-ideal particle packing hinder full densification in the final sintering step. The powder obtained by hydrothermal decomposition of thorium hydroxide shows the highest specific surface area among all (SSA &gt; 100 m<small>²</small> g<small>⁻¹</small>) and reaches a relative density of ∼90% in conventional pressure-less sintering at 1100 °C.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 37","pages":" 6213-6224"},"PeriodicalIF":2.6,"publicationDate":"2025-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ce/d5ce00459d?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145100560","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Advancements and applications in two-dimensional material-assisted epitaxy of semiconductor compounds","authors":"Jianjie Li, Yu Xu, Jianxi Xu, Miao Liu, Tian Xia, Jiangpeng Zhu, Yizhe Huang, Liang Wang, Lei Yao, Jianfeng Wang, Bing Cao and Ke Xu","doi":"10.1039/D5CE00546A","DOIUrl":"https://doi.org/10.1039/D5CE00546A","url":null,"abstract":"<p >The groundbreaking development of semiconductor thin-film materials has played a pivotal role in advancing modern technologies, with extensive applications spanning lighting displays, power electronics, and microwave/RF systems. In vapor-phase epitaxy, the innovative integration of two-dimensional (2D) materials offers revolutionary solutions to address lattice mismatch and thermal expansion mismatch in heteroepitaxial growth: weak van der Waals interactions at interfaces effectively mitigate stress accumulation, while surface state engineering of 2D materials enables precise control over nucleation dynamics. Furthermore, the synergistic relationship between the layer number of 2D materials and substrate polarity allows directional modulation of epitaxial growth. Notably, the breakthrough in detachable transfer of epitaxial layers has unlocked new possibilities for flexible electronics and hybrid integrated devices. This study systematically investigates the unique advantages of 2D materials in optimizing epitaxial growth and expanding device functionalities. By analyzing the heteroepitaxial characteristics of ZnO, GaAs, GaN, and AlN on 2D materials, along with their optoelectronic and high-frequency device applications, we provide a theoretical framework and practical guidance to overcome current technological limitations and outline future research directions.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 37","pages":" 6088-6105"},"PeriodicalIF":2.6,"publicationDate":"2025-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145100548","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":"Effect of electrochemically active surface area on the charge-transfer resistance of layered positive electrode materials","authors":"Kingo Ariyoshi and Toshiyuki Tanaka","doi":"10.1039/D5CE00709G","DOIUrl":"https://doi.org/10.1039/D5CE00709G","url":null,"abstract":"<p >Clarifying the relationship between the electrochemically active surface area and power capability is important for producing high-power batteries. In this study, the impact of particle morphology on the electrochemical kinetics of LiNi<small>_1/3</small>Co<small>_1/3</small>Mn<small>_1/3</small>O<small>₂</small> (NCM) materials was investigated <em>via</em> rate-capability tests and electrochemical impedance spectroscopy using diluted NCM electrodes. In particular, different sizes and shapes of NCM materials were compared. The rate capability was governed by the particle size and shape, which were correlated with the Li-ion diffusion length and electrochemically active surface area. In addition, charge-transfer resistance was inversely proportional to the electrochemically active surface area, highlighting the importance of facet engineering. Therefore, optimising the particle morphology to selectively enhance active surfaces supports high-power and high-rate capabilities.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 37","pages":" 6122-6126"},"PeriodicalIF":2.6,"publicationDate":"2025-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ce/d5ce00709g?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145100550","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"The construction of one-dimensional chain-like coordination polymers and their applications in anode materials for lithium-ion batteries","authors":"Jingwei Liu, Shifa Dang, Xiaolong Cheng, Mengxian Zheng, Xinyi Chen, Weile Kong, Lei Zhang and Shuangyan Wu","doi":"10.1039/D5CE00657K","DOIUrl":"https://doi.org/10.1039/D5CE00657K","url":null,"abstract":"<p >Traditional organic electrode materials are inherently limited by poor cycling stability and low specific capacity. In contrast, coordination polymers (CPs) have shown significant promise as alternative materials due to their rationally engineered structures. By forming coordination bonds between transition metals and organic ligands, CPs create abundant lithium storage sites, thereby overcoming the limitations of conventional organic materials. In this work, two novel one-dimensional CPs [Co(pzca)<small>₂</small>(H<small>₂</small>O)]<small>_<em>n</em></small> (Co-1D) and [Ni(pzca)<small>₂</small>(H<small>₂</small>O)]<small>_<em>n</em></small> (Ni-1D) were synthesized <em>via</em> coordination of pyrazine-2-carboxylic acid (Hpzca) with Co<small>²⁺</small>/Ni<small>²⁺</small> centers. Electrochemical characterization reveals remarkable lithium storage performance. Ni-1D delivers a reversible capacity of 401.6 mA h g<small>⁻¹</small> after 200 cycles at 100 mA g<small>⁻¹</small>, while Co-1D exhibits superior electrochemical behaviour with enhanced capacity retention (596.9 mA h g<small>⁻¹</small>) and near 100% coulombic efficiency. The distinct performance discrepancy between the two CPs originates from their metal-centered redox characteristics and optimized Li<small>⁺</small> diffusion pathways, as evidenced by kinetic analysis and density functional theory calculation. This work provides fundamental insights into designing CP-based anodes with tailored coordination architectures for high-performance lithium-ion batteries.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 37","pages":" 6193-6201"},"PeriodicalIF":2.6,"publicationDate":"2025-09-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145100558","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":"Sources of symmetry in ‘Blind Tests’ crystal structures","authors":"Simon N. Black","doi":"10.1039/D5CE00618J","DOIUrl":"https://doi.org/10.1039/D5CE00618J","url":null,"abstract":"<p >Molecules create crystals <em>via</em> intermolecular interactions that embody long-range order. Previously, close approaches between the aromatic rings of halobenzene molecules, designated ‘Symthons’, were found to be highly effective in creating long-range order in their crystal structures. Here, analysis of 42 ‘blind test’ crystal structures extends the application of ‘Symthons’ to fused rings, heterocycles and five-membered rings. This concept is further adapted to identify hydrogen-bonded approaches which create symmetry. Most of the 42 crystal structures contain at least one Symthon, some of which create long-range order. Other aromatic approaches and hydrogen bonds help to create symmetrical interactions, providing an alternative route to long-range order. In this dataset, hydrogen bonds were both less frequent and less effective at creating long-range order. However, hydrogen bonds were more effective at linking different molecules in salts, hydrates and cocrystals. Implications for nucleation, supramolecular synthons and graph sets are discussed briefly.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 38","pages":" 6314-6323"},"PeriodicalIF":2.6,"publicationDate":"2025-09-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ce/d5ce00618j?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145183987","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Exploring bimodal mesoporous aluminum MOFs: synthesis and defect analysis of rad net topology with imine-based ligand","authors":"Souvik Pal, Ling-I Hung, Wun-Jing Chen, Jiun-Jen Chen, Chun-Chuen Yang and Chia-Her Lin","doi":"10.1039/D5CE00532A","DOIUrl":"https://doi.org/10.1039/D5CE00532A","url":null,"abstract":"<p >Metal–organic frameworks (MOFs) are a versatile class of porous crystalline materials whose properties can be finely tuned through reticular chemistry. Isoreticular expansion, a powerful strategy for increasing pore size without altering framework topology, has enabled the design of MOFs with hierarchical porosity and enhanced functionality. In this study, we report the scalable synthesis and structural characterization of a new aluminum-based MOF, designated AlDMDA-68, constructed using an imine-based dicarboxylate linker 4,4′-(hydrazine-1,2-iylidenebis(methanylylidene))dibenzoic (H<small>₂</small>DMDA). The framework exhibits a <strong>rad</strong> net analogous to MIL-68(Al), featuring dual-channel architectures with pore diameters up to 3.16 nm. Optimization of reaction parameters, including metal-to-ligand (M/L) ratio, yielded phase-pure materials with rod-like morphology. Powder X-ray diffraction and <small>²⁷</small>Al MAS NMR confirmed framework formation and the presence of coordination defects, respectively. Nitrogen sorption measurements revealed a high Brunauer–Emmett–Teller (BET) surface area of 1866 m<small>²</small> g<small>⁻¹</small> and substantial uptake, indicating a hierarchical microporous–mesoporous structure. The material also demonstrated high thermal stability (∼350 °C) and excellent scalability, achieving a fivefold increase in yield without compromising structural integrity. These findings highlight AlDMDA-68 as a promising candidate for various applications and establish elongated imine-based linkers as effective building blocks for designing mesoporous Al-MOFs with tunable functionality.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 38","pages":" 6295-6302"},"PeriodicalIF":2.6,"publicationDate":"2025-09-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145183985","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}