CrystEngComm最新文献

{"title":"Pushing the limits of oxygen balance in pentazolate salts via the theoretical construction of oxidizer-based cocrystal","authors":"Zhenyu Yuan, Chen Yang, Lei Wang and Changlin Zhou","doi":"10.1039/D5CE01076D","DOIUrl":"https://doi.org/10.1039/D5CE01076D","url":null,"abstract":"<p >Designing high-energy-density materials (HEDMs) based on nonmetallic <em>cyclo</em>-pentazolate (<em>c</em>-N<small>₅</small><small>⁻</small>) salts remains challenging because of their low intrinsic density and unfavorable oxygen balance. Here, we introduce a zero-oxygen-balance (based on CO) cocrystal strategy, pairing <em>c</em>-N<small>₅</small><small>⁻</small> salts with energetic oxidizers such as ammonium dinitramide (ADN) and hydrazinium nitroformate (HNF). Using a constrained evolutionary search, two stable cocrystals, [NH<small>₄</small>][N<small>₅</small>]·ADN and [N<small>₂</small>H<small>₅</small>][N<small>₅</small>]·HNF, are predicted. [NH<small>₄</small>][N<small>₅</small>]·ADN is predicted to be most stable in a monoclinic <em>P</em>2<small>₁</small>/<em>c</em> setting, whereas [N<small>₂</small>H<small>₅</small>][N<small>₅</small>]·HNF favors an orthorhombic <em>Pna</em>2<small>₁</small> arrangement; both are reinforced by extensive hydrogen-bond networks. Electronic structure calculations show reduced band gaps relative to the parent salts, indicating increased electronic activity and identifying N–N and N–O bonds as the most labile sites. <em>Ab initio</em> molecular dynamics indicate thermal robustness of the cocrystals on the simulated timescale (up to 800 K). Energetic performance estimated under the same computational protocol yields predicted detonation velocities of 9.61 and 9.82 km s<small>⁻¹</small> and pressures of 39.55 and 42.49 GPa for [NH<small>₄</small>][N<small>₅</small>]·ADN and [N<small>₂</small>H<small>₅</small>][N<small>₅</small>]·HNF, respectively; the detonation velocity values exceed those predicted for the parent salts and for benchmark explosives such as β-CL-20. These results suggest that oxidizer integration <em>via</em> cocrystallization offers a practical route to mitigate the intrinsic limitations of <em>c</em>-N<small>₅</small><small>⁻</small> salts and to guide design of next-generation HEDMs.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 18","pages":" 2920-2926"},"PeriodicalIF":2.6,"publicationDate":"2026-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147872230","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":"Optimized sample-loading method for SERS detection of crystal violet on Ag/ZnO powder: towards rapid and ultrasensitive detection of water contaminants","authors":"A. C. García-Velasco, L. Zamora-Peredo, M. Bizarro, A. Báez-Rodríguez, J. Hernández-Torres, M. A. Díaz-Solís and T. J. Olivares-Silva","doi":"10.1039/D6CE00104A","DOIUrl":"https://doi.org/10.1039/D6CE00104A","url":null,"abstract":"<p >Ultrasensitive and rapid detection of organic pollutants in water is essential for environmental monitoring. Despite advances in SERS substrates, practical use is often limited by sample-loading methods. Our approach enables crystal violet detection at 10<small>⁻¹³</small> M with a total detection time of only 3 min, facilitating practical and fast analysis.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 20","pages":" 3171-3176"},"PeriodicalIF":2.6,"publicationDate":"2026-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148011676","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":"Optimizing conditions for the formation of calcium oxalate trihydrate using the response surface methodology","authors":"Nives Matijaković Mlinarić, Arijana Hamzić, Nikolina Filipović, Jelena Brdarić Kosanović, Imre Szenti, Marija Banožić and Anamarija Stanković","doi":"10.1039/D6CE00201C","DOIUrl":"https://doi.org/10.1039/D6CE00201C","url":null,"abstract":"<p >Calcium oxalate (CaOx), the main component of kidney stones, occurs in several hydrated forms, among which calcium oxalate trihydrate (COT) is a rare and metastable phase believed to act as a transient precursor to the thermodynamically stable monohydrate. In this study, the response surface methodology (RSM), a statistical data analysis method that combines a specific experimental design with mathematical modeling, was applied to quantitatively evaluate and predict the influence of temperature, pH, and ionic strength on the formation of COT. The resulting precipitates were characterized using optical microscopy, scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FTIR), and powder X-ray diffraction (PXRD). The results demonstrate that COT formation is favored at moderate temperatures, while higher temperatures promote the formation of calcium oxalate monohydrate (COM), whereas ionic strength exerts no significant effect under the investigated conditions. Overall, temperature was identified as the dominant parameter governing CaOx hydrate phase selection.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 22","pages":" 3506-3517"},"PeriodicalIF":2.6,"publicationDate":"2026-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2026/ce/d6ce00201c?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148193723","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":"Novel hydroxyl-functionalized 1,2,4-triazole-based oligomers: synthetic approach, photoluminescence and coordination behaviour as uranyl chelators","authors":"Dmytro M. Khomenko, Oleksandr V. Vashchenko, Roman O. Doroshchuk, Viktoriia S. Starova, Mariia Hreben, Valerii Bukhanko, Andrii V. Yatsymyrskyi, Sergiu Shova, Olga Yu. Vassilyeva and Rostyslav D. Lampeka","doi":"10.1039/D6CE00233A","DOIUrl":"https://doi.org/10.1039/D6CE00233A","url":null,"abstract":"<p >The management and recycling of accumulated depleted uranium may benefit from the development of novel organic heterocyclic systems that can be used as ligands for uranyl complexes in advanced materials. Although functionalized 1,2,4-triazoles have shown promise as ligand systems for a variety of transition metals, little is known about their coordination behaviour towards uranyl and the characteristics of the resultant complexes. In the present study, a synthetic strategy to construct functionalized oligo(1,2,4-triazoles) has been developed to prepare mono- (<strong>H<small>₂</small>L<small>¹</small></strong>), bis- (<strong>H<small>₂</small>L<small>²</small></strong>) and tris(1,2,4-triazole)-based oligomers (<strong>H<small>₂</small>L<small>³</small></strong>) bearing hydroxymethyl and hydroxyphenyl substituents. Uranyl complexes [UO<small>₂</small>(L<small>¹</small>)(CH<small>₃</small>OH)]<small>₂</small>·2CH<small>₃</small>OH (<strong>1</strong>), [UO<small>₂</small>(L<small>²</small>)]<small>₂</small>·4DMF (<strong>2</strong>) and [UO<small>₂</small>(HL<small>³</small>)(CH<small>₃</small>COO)]·CH<small>₃</small>OH·H<small>₂</small>O (<strong>3</strong>) were easily synthesized by combining UO<small>₂</small>(CH<small>₃</small>COO)<small>₂</small>·2H<small>₂</small>O with the ligand under suitable conditions. The identical halves of the dinuclear complexes <strong>1</strong> and <strong>2</strong> are bridged by two deprotonated alkoxy groups from the tri- and tetradentate ligands, respectively. In complex <strong>3</strong>, the pendant hydroxymethyl group of (<strong>HL<small>³</small></strong>)<small>⁻</small> remains protonated, impeding dimerization of the molecule. Extensive N/O–H⋯O and C–H⋯N/O hydrogen bonding consolidates supramolecular 3D network structures of the uranyl complexes in the solid state. The behaviour of the ligands and complexes in DMSO solution was investigated using <small>¹</small>H NMR and <small>¹</small>H DOSY NMR spectroscopy, complemented by DFT calculations. Under excitation with UV light (<em>λ</em><small>_ex</small> = 310–311 nm), the ligands in solution give rise to strong broad bands centred near 444 nm with Stokes shifts of ∼133 nm. The photoluminescence quenching observed for <strong>1–3</strong> (1 × 10<small>⁻⁵</small> M, DMSO) as compared to the free ligands was rationalized with the use of DFT calculations performed with the ORCA 6.0.1 program package.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 22","pages":" 3486-3498"},"PeriodicalIF":2.6,"publicationDate":"2026-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148193721","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":"2D Stranski–Krastanov growth of planar AuAg nano-dendrimers for enhanced visible-light plasmonic catalysis","authors":"Qiuxiang Sun, Xiangyu Tong, Xusheng Chen, Zhaoqiang Wang, Xiaohu Wu, Yanyun Ma and Yiqun Zheng","doi":"10.1039/D6CE00228E","DOIUrl":"https://doi.org/10.1039/D6CE00228E","url":null,"abstract":"<p >Plasmonic bimetallic nanostructures with complex morphologies offer enhanced light-harvesting and catalytic properties. Herein, we report the one-pot synthesis of two-dimensional, dendrimer-shaped gold–silver (AuAg) bimetallic nanoparticles <em>via</em> ascorbic acid reduction with the presence of docosyltrimethylammonium chloride and hexamethylenetetramine in an ice-water bath. The synthesized nanoparticles feature a unique planar, branched morphology with arm lengths of approximately 50 nm and trunk diameters of ∼10 nm, as confirmed by electron microscopy. Owing to the localized surface plasmon resonance (LSPR) covering the visible region, we demonstrate their efficacy as plasmonic catalysts under low-power visible light irradiation (590 nm LED). In particular, enhanced catalytic activity was observed in a model reaction compared to dark conditions, which is attributed to the efficient generation and injection of hot electrons from the visible-light-excited plasmonic nanostructures. Finite element method (FEM) electromagnetic simulations corroborate that this specific morphology generates intense localized field enhancements at the branch tips and supports a strong plasmonic response tuned to the visible region. This work highlights the potential of morphologically engineered bimetallic nano-dendrimers as high-performance photocatalysts for sustainable chemistry driven by visible light.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 19","pages":" 3134-3143"},"PeriodicalIF":2.6,"publicationDate":"2026-04-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147967862","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":"Correction: Influence of crystallization solvents on the crystal structures and supramolecular assemblies of a [2]naphthyl-extended pillar[6]arene","authors":"Randa Abd Almoaeen, Mickey Vinodh, Fatemeh H. Alipour and Talal F. Al-Azemi","doi":"10.1039/D6CE90053D","DOIUrl":"https://doi.org/10.1039/D6CE90053D","url":null,"abstract":"<p >Correction for ‘Influence of crystallization solvents on the crystal structures and supramolecular assemblies of a [2]naphthyl-extended pillar[6]arene’ by Randa Abd Almoaeen <em>et al.</em>, <em>CrystEngComm</em>, 2026, <strong>28</strong>, 1331–1338, https://doi.org/10.1039/D5CE01118C.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 18","pages":" 3008-3008"},"PeriodicalIF":2.6,"publicationDate":"2026-04-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2026/ce/d6ce90053d?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147872240","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":"Solvent-free modafinil acid cocrystallization through a green melt-based approach","authors":"Timothy Joseph Hutagaol, Jianmin Zhou, Ziyi Liu, Zhenguo Gao and Junbo Gong","doi":"10.1039/D6CE00119J","DOIUrl":"https://doi.org/10.1039/D6CE00119J","url":null,"abstract":"<p >This study presents a rational crystal engineering strategy for the accelerated, solvent-free preparation of pharmaceutical cocrystals utilizing an integrated approach that combines predictive machine learning (ML) screening with a melt-based Kofler contact strategy. This strategy was applied to modafinil acid, a poorly water-soluble intermediate essential for the synthesis of modafinil and adrafinil. By leveraging thermodynamic principles and process intensification, we developed a solvent-free quantitative method for preparing modafinil acid cocrystal hydrates, successfully eliminating hazardous waste streams. This study bridges sustainable cocrystal design with solvent-free synthesis by integrating quantitative eutectic phase analysis, thereby enabling efficient cocrystal preparation and minimizing conventional trial-and-error screening. Molecular analysis elucidates the intermolecular interactions governing phase stability, while solid-state characterization confirms a four-fold increase in aqueous solubility and a 1.5-fold improvement in phosphate buffer. This integrated workflow offers an efficient, environmentally benign route for the sustainable synthesis of pharmaceutical cocrystals by balancing predictive digital tools with rapid experimental validation.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 21","pages":" 3375-3386"},"PeriodicalIF":2.6,"publicationDate":"2026-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148141611","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":"Spiral-stacked crystal assembly leading to intensified iridescence in poly(trimethylene terephthalate)","authors":"Graecia Lugito, Selvaraj Nagarajan, Widyantari Rahmayanti, H. Ni'mah, Siti Nurkhamida and Eamor M. Woo","doi":"10.1039/D6CE00128A","DOIUrl":"https://doi.org/10.1039/D6CE00128A","url":null,"abstract":"<p >Poly(trimethylene terephthalate) (PTT) is used as a model material to study how the internal 3D crystal structure connects with the surface banded patterns, by using physical and chemical etching methods to better reveal the crystal arrangement. Narrow crystal shells are observed to be sandwiched within the crevices of successive bands in chemically etched PTT. Furthermore, the distinct gaps between adjacent crystal bands revealed by physical etching provide additional evidence for discontinuous radial growth between bands. Spiral-spin assembly with periodic conical banded aggregates is observed, in which periodicity originated from a core nucleus whose initial geometry guided the formation of different types of banded crystals. The intensified iridescence arises from the highly ordered lamellar arrangement.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 20","pages":" 3177-3187"},"PeriodicalIF":2.6,"publicationDate":"2026-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148011677","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":"A robust ditopic enaminone- and hydrazone-linked amine-functionalized porous organic cage for effective permanganate capture and conversion","authors":"Jiajia Sheng, Yanan Guo, Guoshi Zhang, Wenjing Wang, Kongzhao Su and Daqiang Yuan","doi":"10.1039/D5CE01205H","DOIUrl":"https://doi.org/10.1039/D5CE01205H","url":null,"abstract":"<p >Potassium permanganate (KMnO<small>₄</small>) is widely employed as an oxidizing agent for water purification and pollutant removal. However, the residual MnO<small>₄</small><small>⁻</small> in water presents substantial health risks, and thus the efficient removal of aqueous MnO<small>₄</small><small>⁻</small> has emerged as a major research focus. Herein, we present a novel amine-containing triangular prism-shaped [3 + 6] porous organic cage (POC) adsorbent, named <strong>DPOC-1</strong>. It is assembled from three tetraformyl-functionalized calix[4]resorcinarenes and six heteroditopic 3,4-diaminobenzhydrazide organic synthons through Schiff-base chemistry. SCXRD analysis reveals that <strong>DPOC-1</strong> contains a large cavity volume of up to ∼1500 Å<small>³</small>, two large guest-accessible windows with a maximum diameter of 0.75 nm, as well as abundant nitrogen and oxygen chelating sites surrounded by its windows. Leveraging these advantageous features, combined with its specific surface area of up to approximately 700 m<small>²</small> g<small>⁻¹</small>, <strong>DPOC-1</strong> demonstrates exceptional efficiency in capturing aqueous MnO<small>₄</small><small>⁻</small>. It achieves a removal rate exceeding 99% within 3 minutes and shows excellent recyclability through a dual adsorption–reduction mechanism. Specifically, the material maintains nearly 90% adsorption efficiency even after 10 consecutive cycles, and a portion of the absorbed MnO<small>₄</small><small>⁻</small> is subsequently converted into value-added Mn<small>₂</small>O<small>₃</small>. This study offers a novel strategic approach for utilizing POC adsorbents in the remediation of heavy metal oxyanion pollution, simultaneously enabling resource recovery.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 22","pages":" 3518-3525"},"PeriodicalIF":2.6,"publicationDate":"2026-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148193724","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":"Structure and luminescence colour change of an iridium(iii) bis-terpyridine complex crystal triggered by water sorption/desorption","authors":"Yusuke Endo, Mio Kondo, Tomoe Nakamura, Shingo Hattori, Akiko Sekine, Sosuke Kojo and Kazuteru Shinozaki","doi":"10.1039/D6CE00194G","DOIUrl":"https://doi.org/10.1039/D6CE00194G","url":null,"abstract":"<p >A cationic complex crystal of [Ir(tpy)<small>₂</small>]Br<small>₃</small>·7H<small>₂</small>O (tpy = 2,2′:6′,2″-terpyridine) shows luminescence vapochromism as a reversible conversion between yellow and orange emissions in response to heating/cooling. X-ray crystallography reveals that [Ir(tpy)<small>₂</small>]Br<small>₃</small>·7H<small>₂</small>O exists as a triclinic crystal system, comprising Ir(<small>III</small>) complex layers and 2D hydrophilic sheets of H<small>₂</small>O and Br<small>⁻</small>. The orange emissive crystal is determined to be the orthorhombic [Ir(tpy)<small>₂</small>]Br<small>₃</small>·2H<small>₂</small>O, comprising 1D hydrophilic channels of H<small>₂</small>O and Br<small>⁻</small>, with Br<small>⁻</small> in close proximity to the Ir(<small>III</small>) complex. The yellow emission of [Ir(tpy)<small>₂</small>]Br<small>₃</small>·7H<small>₂</small>O is due to the dual emission from the ligand-centered π–π* transition and the Br<small>⁻</small>-to-ligand charge transfer (XLCT). The π–π* emission is quenched by the switching to the XLCT emission by the close approach of Br<small>⁻</small> to Ir(<small>III</small>) complex resulting from the H<small>₂</small>O desorption. The reversible H<small>₂</small>O sorption/desorption results in not only the luminescence colour change but also the drastic structural change between triclinic and orthorhombic crystal systems. The weak stimulus of H<small>₂</small>O sorption/desorption triggers the phase transition of the Ir(<small>III</small>) complex crystal; 5 H<small>₂</small>O molecules are incorporated into the 1D channel of the [Ir(tpy)<small>₂</small>]Br<small>₃</small>·2H<small>₂</small>O crystal to change the Ir–Br<small>⁻</small> framework from orthorhombic to triclinic, and inversely, the elimination of 5 H<small>₂</small>O molecules from the 2D hydrophilic sheet in [Ir(tpy)<small>₂</small>]Br<small>₃</small>·7H<small>₂</small>O contributes to the reconstruction of the hydrophilic channel along with the reversion of the framework to orthorhombic.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 20","pages":" 3259-3266"},"PeriodicalIF":2.6,"publicationDate":"2026-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2026/ce/d6ce00194g?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148011691","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}