CrystEngComm最新文献

{"title":"Cationic substitution engineering induces a new quaternary chalcogenide in the A–MIIIA–MIVA–Q system for optical crystal applications†","authors":"Yue Wang, Xuezhong Li, Zihao Lou and Yongfang Shi","doi":"10.1039/D5CE00016E","DOIUrl":"https://doi.org/10.1039/D5CE00016E","url":null,"abstract":"<p >A new quaternary chalcogenide in the A–M<small>^IIIA</small>–M<small>^IVA</small>–Q system, CsGaGe<small>₃</small>S<small>₈</small>, was synthesized <em>via</em> a high-temperature solid-state reaction. It crystallized in the monoclinic system (space group <em>P</em>2<small>₁</small>/<em>c</em>) and featured 2D ∞<small>²</small> [(Ga/Ge)<small>₈</small>S<small>₁₆</small>]<small>²⁻</small> layers, with Cs<small>⁺</small> ions occupying the interlayer regions. The material exhibited excellent thermodynamic stability (up to 600 °C) and a broad UV-vis-IR transmission range (0.33–23 μm), with a band gap of 3.38 eV and a birefringence of 0.043 at 546 nm. Compared to AgGaS<small>₂</small>, CsGaGe<small>₃</small>S<small>₈</small> offers a wider transmission range and larger birefringence, making it a promising candidate for infrared birefringent crystals. First-principles calculations further elucidated its structure–property relationship.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 20","pages":" 3378-3385"},"PeriodicalIF":2.6,"publicationDate":"2025-04-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144090780","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":"Advancing zeolite design via ionic liquid templating approach","authors":"Tianzhao Liu, Xuemin Li, Owen J. Curnow, Jungkyu Choi and Alex C. K. Yip","doi":"10.1039/D5CE00253B","DOIUrl":"https://doi.org/10.1039/D5CE00253B","url":null,"abstract":"<p >Ionic liquids (ILs) have emerged as versatile tools in zeolite synthesis and structural modification, providing precise control over crystallization, morphology, porosity, and framework design. Their physicochemical properties, such as low vapor pressure, high thermal stability, and tunable polarity, enable their role as solvents, structure-directing agents (SDAs), porogens, and post-synthetic modifiers in zeolite formation. This article highlights the use of ILs in functionalized zeolite synthesis and modification, assessing their impact on zeolite topology, morphology, and the development of functionalized zeolites, including nanosized, hierarchical, and application-driven frameworks. By discussing recent advancements, we provide insights into the rational design and discovery of novel zeolite materials, fostering future innovations in catalysis, adsorption, and separation technologies.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 20","pages":" 3164-3179"},"PeriodicalIF":2.6,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144090918","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":"Tb3+/Ce3+-codoped LiLuF4 nanocrystal glasses for high-resolution X-ray imaging†","authors":"Wenhao Yang, Jintao Xu, Yi Zheng, Xin Huang, Min Chen, Shuaihua Wang and Shaofan Wu","doi":"10.1039/D5CE00086F","DOIUrl":"https://doi.org/10.1039/D5CE00086F","url":null,"abstract":"<p >Glass-based scintillators, with low cost and large-scale preparation, have received extensive attention in medical and industrial X-ray imaging applications. However, the undesirable scintillation performance of scintillation glasses limits their further application, since precipitating nanocrystals with high luminescence efficiency and large density in glass remains difficult. Here, an ion-covalent fluoroaluminate–borate glass network structure is constructed to precipitate co-doped LiLuF<small>₄</small> nanocrystals. Due to the nanoscale and good dispersion of precipitated crystals, LiLuF<small>₄</small> nanocrystal glasses (NGs) maintain a high visible light transmission property. The scintillation performances of LiLuF<small>₄</small> NGs are improved by optimal heat treatment processing and co-doping of Ce<small>³⁺</small> and Tb<small>³⁺</small>. Specifically, a high light yield of 14 508 ph MeV<small>⁻¹</small> and outstanding radiation resistance are reached in the optimal NGs, which is attributed to the uniformly distributed LiLuF<small>₄</small>:Tb,Ce nanocrystals. Moreover, large-scale NGs exhibit an outstanding X-ray imaging performance for various objects, achieving a high spatial resolution of 18.4 Lp mm<small>⁻¹</small>. Through a nanocrystal enhancing strategy, the present report explores novel high-performance and cost-effective glass-based scintillators and demonstrates LiLuF<small>₄</small>:Tb,Ce NGs as a promising candidate for next-generation X-ray imagers.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 19","pages":" 3048-3053"},"PeriodicalIF":2.6,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143944072","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":"Study on the melt/crystal interface in large-size yttrium aluminum garnet crystal growth","authors":"Ruixian Wang, Qingli Zhang, Mingliang Yang, Yi He, Xiaofei Wang, Yu Sun and Deming Zhang","doi":"10.1039/D5CE00069F","DOIUrl":"https://doi.org/10.1039/D5CE00069F","url":null,"abstract":"<p >It is crucial to control the melt/crystal (m/c) interface and ensure that it is convex to achieve high-quality and large-size yttrium aluminum garnet (YAG) laser crystal growth using the Czochralski method. The enthalpy-porosity method is used to describe the m/c interface, and the reasons for the formation of the W-shaped m/c interface during large-size YAG laser crystal growth are studied. The results show that the W-shaped m/c interface is caused by the inflection point in the variation of the temperature gradient along the crystal radius. The interface formation can be avoided by reducing the thermal insulation lid aperture, crucible lid aperture, crystal rotation rate, and crystal diameter. An enclosed vortex is formed near the W-shaped m/c interface, which hinders impurity transportation, causes inclusion defects, and increases thermal stresses in the crystal. A convex m/c interface is beneficial for reducing thermal stress in crystals. Using an iridium crucible with a diameter of 400 mm, the W-shaped m/c interface observed during large-size YAG crystal growth by the Czochralski method closely matches the results of numerical simulations. We successfully grew YAG crystals with a diameter of 140 mm using the improved technique. These results provide guidance for large-size YAG laser crystal growth.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 18","pages":" 2910-2919"},"PeriodicalIF":2.6,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143908495","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":"Calix[4]arene-supported trigonal and square prisms of Mn and Na†","authors":"Lucinda R. B. Wilson, Scott J. Dalgarno and Euan K. Brechin","doi":"10.1039/D5CE00285K","DOIUrl":"https://doi.org/10.1039/D5CE00285K","url":null,"abstract":"<p >The heterometallic tricapped trigonal prism [Mn<small>^III</small><small>₃</small>Na<small>₆</small>(TBC[4])<small>₃</small>(CO<small>₃</small>)(Cl)(dmso)<small>₇</small>]·5MeCN ([Mn<small>₃</small>Na<small>₆</small>]; <strong>1</strong>·5MeCN) and the related heterometallic tetracapped square prism [Mn<small>^III</small><small>₄</small>Mn<small>^II</small><small>₂</small>Na<small>₆</small>(bisTBC[4])<small>₂</small>(CO<small>₃</small>)<small>₂</small>(Cl)<small>₂</small>(dmf)<small>₈</small>(MeOH)<small>_1.2</small>(H<small>₂</small>O)<small>_0.8</small>]·6MeCN ([Mn<small>₆</small>Na<small>₆</small>]; <strong>2</strong>·6MeCN), are isolated using <em>p</em>-<small>^<em>t</em></small>Bu-calix[4]arene (H<small>₄</small>TBC[4]) and 2,2′-bis-<em>p</em>-<small>^<em>t</em></small>Bu-calix[4]arene (H<small>₈</small>-bisTBC[4]), respectively. In the former the Mn<small>^III</small> ions sit in the TBC[4] polyphenolic pockets, forming three Mn-TBC[4] metalloligands that cap the square faces of the prism, whose vertices contain the six Na ions. Introduction of the bis-calix[4]arene enables expansion of the main building block from three Mn-TBC[4] metalloligands in <strong>1</strong> to four Mn-TBC[4] metalloligands in <strong>2</strong>. The result is the formation of a square prism of Na/Mn<small>^II</small> ions, with four of the square faces capped with Mn<small>^III</small> ions. Dc magnetic susceptibility and magnetisation measurements reveal paramagnetism in <strong>1</strong> and weak antiferromagnetic exchange interactions in <strong>2</strong>.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 19","pages":" 3041-3047"},"PeriodicalIF":2.6,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ce/d5ce00285k?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143944071","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":"Understanding surface morphology evolution in magnetron sputtered AlN templates: mitigating tensile stress and enhancing crystal quality†","authors":"Li Jiang, Jianwei Ben, Ke Jiang, Shanli Zhang, Tong Wu, Zikai Nie, Entao Zhang, Shunpeng Lu, Xiaojuan Sun and Dabing Li","doi":"10.1039/D5CE00027K","DOIUrl":"https://doi.org/10.1039/D5CE00027K","url":null,"abstract":"<p >The thickness and surface morphology of aluminum nitride (AlN) templates are crucial for evaluating their quality and suitability for device applications. However, the relationship between these two factors remains unclear for AlN templates grown <em>via</em> magnetron sputtering. This study systematically investigates the surface restructuring mechanisms in AlN films during thickness progression, revealing a stress-driven morphological transition. As film thickness increases, accumulated tensile stress exceeding ∼0.5 GPa triggers the spontaneous formation of “flower-like” surface patterns through stress relief. While mitigating further stress buildup, this morphological transformation degrades crystalline quality post-high-temperature annealing. Through strategic optimization of sputtering thermodynamics, we successfully preset compressive stress in AlN films and extended the critical thickness for morphological degradation to 2 μm. The resulting high-quality thick AlN films exhibit simultaneously improved surface continuity and enhanced crystalline perfection. These results provide valuable insights into the stress-morphology interactions in sputtered AlN films, offering new strategies for optimizing AlN template growth and enhancing the performance of AlN-based devices.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 18","pages":" 2895-2901"},"PeriodicalIF":2.6,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143908486","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":"Polymorphism phenomenon of the naphthyl-containing N-salicylidenaniline derivative: syntheses, crystal structures, optical properties, and theoretical calculations†","authors":"Elizaveta V. Panova, Julia K. Voronina, Asmet N. Azizova, Ömer Faruk Tutar, Ghodrat Mahmoudi and Damir A. Safin","doi":"10.1039/D5CE00191A","DOIUrl":"https://doi.org/10.1039/D5CE00191A","url":null,"abstract":"<p >In the present study, we report on the synthesis and an in-depth investigation of two polymorphic modifications of the naphthyl-containing <em>N</em>-salicylidenaniline derivative, namely <em>N</em>-naphthyl-3-methoxysalicylideneimine (<strong>HL</strong>). In particular, a direct condensation reaction of 3-methoxysalicylaldehyde with 1-naphthylamine in the ethanolic medium allowed to produce crystals of polymorph I of <strong>HL</strong> of the monoclinic space group <em>P</em>2<small>₁</small>/<em>c</em>, while a mixture of <strong>HL</strong> and Zn(OAc)<small>₂</small> in the ethanolic medium yielded crystals of polymorph II of <strong>HL</strong> of the orthorhombic space group <em>Pbca</em> upon slow evaporation of the solvent. Furthermore, a solvent-free grinding reaction of 3-methoxysalicylaldehyde with 1-naphthylamine also produced polymorph I of <strong>HL</strong>. In the literature, a polymorph of <strong>HL</strong>, crystallized in the monoclinic space group <em>P</em>2<small>₁</small>/<em>c</em>, was reported; however, this polymorph contains two molecules of <strong>HL</strong> in the asymmetric unit and was obtained by recrystallization from MeOH. Additionally, in the literature, the other polymorph of the triclinic space group <em>P</em><img> with four molecules in the asymmetric unit has also been reported, which was produced through solvent-free grinding or by employing acetonitrile in the recrystallization process. The solids synthesized in this study were characterized using IR and <small>¹</small>H NMR spectroscopy. Their crystal structures and phase purity were determined <em>via</em> single-crystal and powder X-ray diffraction, respectively. The crystal packing of both polymorphs was further analyzed in detail through Hirshfeld surface analysis. To evaluate the optical properties of the compound, diffuse reflectance spectroscopy (solid state) and UV–vis spectroscopy combined with spectrofluorimetry (solution state) were employed. Additionally, density functional theory (DFT) calculations were conducted to provide deeper insights into the structural features and optical behavior of <strong>HL</strong>.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 21","pages":" 3502-3516"},"PeriodicalIF":2.6,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144140027","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":"Designing of self-assembled supramolecular frameworks for recognition of anion–water clusters: recent highlights","authors":"Oiyao Appun Pegu and Gopal Das","doi":"10.1039/D5CE00122F","DOIUrl":"https://doi.org/10.1039/D5CE00122F","url":null,"abstract":"<p >This highlight discusses recent advancements in anion coordination chemistry since 2015, specifically focusing on designing artificial receptors capable of recognizing anion–water clusters. It also addresses the challenges encountered in this field and explores the implications for biological and environmental applications. The solid-state recognition of anion–water clusters, along with detailed structural analyses using single-crystal X-ray diffraction (SC-XRD), is summarized in this article. The discussions explore the different dimensionalities of the anions and the recognition of their corresponding anion–water clusters.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 19","pages":" 2964-2978"},"PeriodicalIF":2.6,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143944043","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":"Computational insights on dynamic disorder in molecular crystals – from electron structure over phonons to thermodynamics","authors":"Ctirad Červinka","doi":"10.1039/D5CE00209E","DOIUrl":"https://doi.org/10.1039/D5CE00209E","url":null,"abstract":"<p >Quantum-chemical nature of molecular interactions and atomic vibrations imparts a ubiquitous internal dynamics even to solid molecular materials that appear as very rigid from the macroscopic point of view. Existence of flat potential energy basins related to dynamic degrees of freedom in molecular crystals usually gives birth to large-amplitude motions of molecular segments or entire molecules that is commonly recognized as dynamic disorder. Computational chemistry offers suitable approaches for sampling these potential energy surfaces, subsequently enabling to model atomic displacements related to disorder and contributions of this internal dynamics to macroscopic material properties such as entropy, volatility, solubility, plasticity or conductivity. This highlight article presents a mosaic of recent research results which were achieved thanks to the computational methods playing a perfectly complementary role to experimental approaches. Observed material properties and the either beneficial or detrimental impact of dynamic disorder thereon can be then interpreted at the atomic level which naturally contributes to a better understanding of the underlying phenomena and enables to rationalize future material design. This highlight article illustrates the impact of dynamic disorder in the fields of barocaloric materials for heat management, active pharmaceutical ingredients and organic molecular semiconductors. Such a scope enables to account for how the dynamic disorder manifests itself in modelling thermodynamic or spectroscopic properties, phase behavior, electron structure and charge transport in molecular crystals.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 18","pages":" 2778-2794"},"PeriodicalIF":2.6,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ce/d5ce00209e?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143908480","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":"Vacuum-sintered Al2O3:Cr3+ transparent ceramics as cost-effective alternatives to single-crystal ruby†","authors":"Yikun Zhang, Pan Hu, Yongfu Liu, Jianfeng Sun and Jun Jiang","doi":"10.1039/D5CE00327J","DOIUrl":"https://doi.org/10.1039/D5CE00327J","url":null,"abstract":"<p >Al<small>₂</small>O<small>₃</small>:Cr<small>³⁺</small> ruby is one of the most popular materials for lasers because it has unique optical and physical properties. How to obtain Al<small>₂</small>O<small>₃</small>:Cr<small>³⁺</small> efficiently and economically remains a challenge. In this study, Al<small>₂</small>O<small>₃</small>:Cr<small>³⁺</small> transparent ceramics were prepared through a traditional solid-state process in a vacuum environment. A high transmittance of 76.8% at 1200 nm, approaching that of single crystals, can be reached in the pure Al<small>₂</small>O<small>₃</small> transparent ceramic. The photoluminescence, micromorphology, thermal conductivity, and mechanical characteristics of Al<small>₂</small>O<small>₃</small>:Cr<small>³⁺</small> transparent ceramics were studied. A ruby with a thermal conductivity of about 38 W m<small>⁻¹</small> K<small>⁻¹</small> and a high hardness of 1859 HV was prepared. These results indicate that Al<small>₂</small>O<small>₃</small>:Cr<small>³⁺</small> transparent ceramics have broad prospects to serve as a substitute for Al<small>₂</small>O<small>₃</small>:Cr<small>³⁺</small> single crystals in certain fields.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 19","pages":" 3134-3142"},"PeriodicalIF":2.6,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143944084","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}