Crystal Growth & Design最新文献

{"title":"Post-crystallization Rearrangement of Crystal Architecture, Intermolecular Interactions, and Nucleotide Conformation in Adenosine Monophosphates Crystals Induced by Single Crystal-to-Single Crystal Dehydration","authors":"Oskar Kaszubowski*,&nbsp; and ,&nbsp;Katarzyna Ślepokura,&nbsp;","doi":"10.1021/acs.cgd.5c0049010.1021/acs.cgd.5c00490","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00490https://doi.org/10.1021/acs.cgd.5c00490","url":null,"abstract":"<p >In this paper, we present the results of structural studies of three adenosine monophosphates: 5′-AMP, 3′-AMP, and 2′-AMP. They concern extensive experiments to obtain new crystalline forms of the indicated nucleotides by both solution crystallization and temperature-induced dehydration. Recognizing the need for a more complete description of the nature of these systems in the solid state, as very poorly known in terms of structure compared to other nucleotides, we obtained several hydrated and anhydrous crystalline varieties in the acid form. Through a detailed analysis of the architecture of the crystals as well as the intermolecular interactions, we identified the main supramolecular tendencies of these compounds in the solid state as well as their particular preferences for the formation of hydrogen bonds, especially through adenine and phosphate groups. Among other things, it takes into account the role of water molecules in creating individual interactions between nucleotides. At the same time, we perceived an extraordinary conformational flexibility of adenylyl nucleotides upon partial or complete loss of water from the crystals. Many of the geometries appear to be extremely rare and have not been observed before in these systems. We emphasize the uniqueness of hydrated adenylyl nucleotide crystals in the context of the dehydration experiments (following the single crystal-to-single crystal transformation) and point out the extraordinary usefulness of this technique in the light of the search for new crystal forms and structural studies.</p><p >Single crystal-to-single crystal dehydration has been demonstrated to be a useful method for obtaining anhydrous varieties of adenylyl nucleotides. The resulting crystal forms are characterized by significantly altered crystal architecture, intermolecular interactions, and nucleotide conformation due to post-crystallization structural reorganization.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 12","pages":"4586–4600 4586–4600"},"PeriodicalIF":3.2,"publicationDate":"2025-06-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.cgd.5c00490","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144305682","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Accelerating Zeolite Crystallization under High External Hydrostatic Pressure","authors":"Raquel Simancas,&nbsp;Masatora Sakakibara,&nbsp;Ryo Asayama,&nbsp;Masato Katsuyama,&nbsp;Masanori Takemoto,&nbsp;Yasuo Yonezawa,&nbsp;Tatsuya Okubo and Toru Wakihara*,&nbsp;","doi":"10.1021/acs.cgd.5c0048210.1021/acs.cgd.5c00482","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00482https://doi.org/10.1021/acs.cgd.5c00482","url":null,"abstract":"<p >Hydrostatic pressure, an often-overlooked parameter in the hydrothermal synthesis of zeolite, has been shown to influence crystallization significantly. This study systematically investigates the role of external hydrostatic pressure on the synthesis of two aluminosilicate zeolites: (1) MFI-type zeolites from clear and milky solutions and (2) FAU-type zeolites from an amorphous aluminosilicate precursor. Applying external hydrostatic pressure significantly accelerates zeolite formation in both systems. Utilizing a two-step heating protocol under autogenous conditions and high hydrostatic pressures (200 MPa for MFI and 800 MPa for FAU), we demonstrate that pressure application during the early synthesis stages dramatically enhances nucleation frequency. This leads to faster crystallization and smaller, more uniformly distributed crystals. Furthermore, the findings reveal the potential of hydrostatic pressure to control critical material properties, including crystal size, crystallinity, and nucleation frequency. By elucidating these effects, this study advances the fundamental understanding of zeolite crystallization mechanisms and provides more tools for the rational design of customized zeolites for catalytic and other applications.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 12","pages":"4577–4585 4577–4585"},"PeriodicalIF":3.2,"publicationDate":"2025-06-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144305787","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Melting Point Prediction of Organic Crystals Using Direct Molecular Dynamics Simulations","authors":"Nahyun Chi,&nbsp;Jungim Han,&nbsp;Joonghee Won and Jun Soo Kim*,&nbsp;","doi":"10.1021/acs.cgd.4c0175310.1021/acs.cgd.4c01753","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01753https://doi.org/10.1021/acs.cgd.4c01753","url":null,"abstract":"<p >Accurate melting point prediction is essential for investigating the molecular mechanisms of crystal growth and melting using molecular dynamics (MD) simulations. Here, we assess melting point predictions from direct MD simulations of nitromethane and acetic acid. This study has three objectives: to evaluate popular force fields (CGenFF, OPLS, GAFF), to assess various MD approaches (simulations of solid/liquid, vapor/solid/liquid/vapor, vapor/solid/vapor, and solid alone), and to compare the crystal growth and melting of both compounds, focusing specifically on the time scale and anisotropy. Our results indicate that none of the popular force fields accurately predict melting points, highlighting the need for improvement. All MD simulation approaches yielded consistent melting points of either compound, except for the solid-alone simulation, while continuous heating of the vapor/solid/vapor system proved effective. The time scales of crystal growth and melting differ significantly between the molecules: 20 ns for nitromethane and 200 ns for acetic acid. Anisotropy in crystal growth and melting is non-negligible and much more pronounced for acetic acid compared to nitromethane. These findings offer practical considerations for simulating melting phenomena in molecular crystals using MD.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 12","pages":"4169–4177 4169–4177"},"PeriodicalIF":3.2,"publicationDate":"2025-06-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144305967","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Understanding the Nature and Energetics of C–H···F Interactions in Crystalline Propamides","authors":"Pratik Dey,&nbsp;Rohit Bhowal,&nbsp;Saikat Kumar Seth* and Deepak Chopra*,&nbsp;","doi":"10.1021/acs.cgd.5c0015210.1021/acs.cgd.5c00152","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00152https://doi.org/10.1021/acs.cgd.5c00152","url":null,"abstract":"<p >Intermolecular interactions play a pivotal role in crystal engineering, enabling the creation of novel materials with tailored properties. While strong hydrogen bonds have traditionally been the primary focus, recent attention has shifted toward weaker interactions, such as C–H···F interactions. Fluorine, previously believed to be incapable of forming hydrogen bonds, has now been recognized for its ability to engage in weak C–H···F interactions, significantly influencing crystal packing. This study explores the intricate nature of C–H···F interactions and their relationship in the presence of other intermolecular interactions. We have synthesized and structurally characterized six new fluorine-containing organic compounds and examined how the positions of fluorine and trifluoromethyl groups (<i>ortho</i>, <i>meta</i>, and <i>para</i>) affect intermolecular interactions. The solid-state structures of these compounds have been explored by investigating the noncovalent interactions present in the crystal. The weak C–H···F interactions, shaped by the electronic environment and the acidity of the donor hydrogen atoms, contribute to the enhanced stability of the crystal structure. To quantify these interactions, we have evaluated the lattice energies via PIXELC, performed the topological analysis via the QTAIM approach, and analyzed the molecular electrostatic potential (MESP) as well. The thermal stability of the compounds has been assessed in the context of noncovalent interactions present in the crystal structure. By elucidating the role of C–H···F interactions, this research aims to contribute to the advancement of supramolecular chemistry and crystal engineering of interactions involving organic fluorine. The study investigates only six fluorinated compounds, which significantly limits its ability to represent the broader and more complex trends within crystal engineering.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 12","pages":"4263–4282 4263–4282"},"PeriodicalIF":3.2,"publicationDate":"2025-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144305680","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Effect of Ultrasound Standing Wave-Induced Acoustophoresis in Monoglyceride Oleogel Structuration","authors":"Petri Lassila*,&nbsp;Thomas Zinn,&nbsp;Jere Hyvönen,&nbsp;Enriqueta Noriega Benitez,&nbsp;Paavo Penttilä,&nbsp;Ari Salmi and Fabio Valoppi*,&nbsp;","doi":"10.1021/acs.cgd.5c0029110.1021/acs.cgd.5c00291","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00291https://doi.org/10.1021/acs.cgd.5c00291","url":null,"abstract":"<p >Ultrasound standing waves (USW) produce a force capable of displacing micrometer-sized free-flowing particles in a fluid, wherein this phenomenon is also referred to as acoustophoresis. However, the effect of acoustophoresis on dynamically changing and growing crystal networks is unclear. An example of such a system are monoglyceride (MG)-based oleogels, which are free-flowing lipids (e.g., vegetable oils) structured with a lipid-crystal network. In this work, we use MG oleogels as an example system to investigate the acoustophoretic effect on the structuration of a growing crystal network. For this purpose, multifaceted characterization is conducted utilizing optical and coded excitation scanning acoustic microscopy as well as small-angle X-ray scattering, respectively. The optical microscopy results show that USW produces local density differences of the structuring crystalline material and induces the orientation of the MG platelets. X-ray diffraction measurements confirm these findings and show a 23% average increase in MG platelet correlation length, which can be linked to platelet thickness, as well as an increase in the MG nanoplatelet surface smoothness. These findings produce a foundation for better understanding the effect of acoustophoresis in dynamically developing lipid-based materials and illuminate the mechanical changes that arise because of USW treatment.</p><p >Ultrasound standing waves (USW) generate forces displacing micrometer-sized particles in fluid─a phenomenon called acoustophoresis. Its impact on evolving crystal networks is unexplored. Using monoglyceride oleogels, we analyze USW effects on crystal growth via optical/acoustic microscopy and SAXS. Results reveal USW-induced density variations, platelet alignment, 23% increase in correlation length, and enhanced surface roughness, elucidating mechanical changes in lipid-based materials.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 12","pages":"4394–4404 4394–4404"},"PeriodicalIF":3.2,"publicationDate":"2025-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.cgd.5c00291","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144305679","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Chain Motifs of Acid Molecules Formed by Symmetric O···H···O and Asymmetric O–H···O Hydrogen Bonds for Salts of Miconazole with Isomeric Pyridinedicarboxylic Acids","authors":"Anna Ben,&nbsp;Justyna Dominikowska,&nbsp;Béla Fiser and Lilianna Chęcińska*,&nbsp;","doi":"10.1021/acs.cgd.5c0023910.1021/acs.cgd.5c00239","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00239https://doi.org/10.1021/acs.cgd.5c00239","url":null,"abstract":"<p >Single-crystal X-ray structures of four new salts of miconazole with isomeric pyridine-2,<i>n</i>-dicarboxylic acids (<i>n</i> = 3, 4, 5, 6) are described. These structures exhibit chain substructures formed by acid molecules, highlighting their role as favorable motifs in the supramolecular architectures of multicomponent crystals. Symmetric O···H···O hydrogen bonds drive the formation of unique polymeric chain motifs, whereas asymmetric O–H···O hydrogen bonds generate common monoperiodic supramolecular chains. Both types of interactions are characterized using the quantum theory of atoms in molecules (QTAIM) approach. The QTAIM analysis reveals significant differences in the properties of these two types of hydrogen bonds, indicating that symmetric hydrogen bonds are significantly stronger and more covalent in nature than asymmetric ones. Furthermore, for molecular pairs extracted from polymeric chain substructures, DFT calculations are employed to describe the proton-transfer profile and rationalize the formation of symmetric interactions in the solid state.</p><p >This study reports the crystal structures of miconazole salts with isomeric pyridine-2,<i>n</i>-dicarboxylic acids (<i>n</i> = 3, 4, 5, 6). Supramolecular architectures highlight the role of chain substructures formed by acid molecules, where symmetric O···H···O interactions facilitate unique polymeric chain motifs and asymmetric O−H···O interactions generate common monoperiodic chains. QTAIM analysis reveals distinct differences in the properties of these two types of interactions.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 12","pages":"4348–4359 4348–4359"},"PeriodicalIF":3.2,"publicationDate":"2025-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.cgd.5c00239","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144305681","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Cooling Crystallization of Sulfamethazine-Acetylsalicylic Acid Cocrystal: Estimating Nucleation Kinetics and Real-Time Phase Identification","authors":"Anindita Saha,&nbsp;Sameer V. Dalvi,&nbsp;Aijaz A. Dar and Jose V. Parambil*,&nbsp;","doi":"10.1021/acs.cgd.5c0043310.1021/acs.cgd.5c00433","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00433https://doi.org/10.1021/acs.cgd.5c00433","url":null,"abstract":"<p >Cooling cocrystallization of 1:1 sulfamethazine-acetylsalicylic acid (SMZ-ASA) cocrystal from acetonitrile is investigated based on the ternary phase diagrams (TPDs) established at 5, 15, 25, and 35 °C. Nucleation kinetics of the cocrystal and pure coformers analyzed using classical nucleation theory (CNT) revealed that the nucleation rate of the cocrystal is significantly lower, approximately 1/111 times that of pure ASA and 1/21 times that of SMZ at similar supersaturations. Cooling cocrystallization was scaled up from 20 mL to 2 L, transitioning from a magnetically stirred to an overhead-stirred system. This scale-up facilitated the study of nucleation and the successful production of cocrystals in larger volumes. Cooling in the stable cocrystal region in the TPD produced pure cocrystals. Cooling crystallization in the SMZ + cocrystal region near the SMZ invariant point in TPD led to the formation of pure cocrystal instead of SMZ-cocrystal mixture due to the influence of nucleation kinetics. Conversely, in the ASA + cocrystal region near the ASA invariant point, a mixed solid phase was obtained. In-situ Raman spectroscopy revealed that pure ASA nucleated first, followed by cocrystal formation approximately 30 min later.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 12","pages":"4521–4530 4521–4530"},"PeriodicalIF":3.2,"publicationDate":"2025-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144305848","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Brilliantly Red: The Structure of Carmine","authors":"Erik Svensson Grape*,&nbsp;Tom Willhammar and A. Ken Inge,&nbsp;","doi":"10.1021/acs.cgd.5c0018510.1021/acs.cgd.5c00185","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00185https://doi.org/10.1021/acs.cgd.5c00185","url":null,"abstract":"<p >Carmine is a red pigment made from dried cochineal, a scale insect that has been a source of brilliant scarlet reds in clothing and art for more than two millennia, with records dating back to 700 BC. Since the 16th century, it has been intensely traded all over the world and was one of the most important trade goods for the Spanish empire at its economic peak. Despite still being used on an industrial scale, with hundreds of metric tonnes produced annually, the exact molecular and crystal structures of the dyestuff remains undetermined. Notably, both modern-day commercial carmine and pigments prepared following historical recipes show strikingly similar diffraction patterns, indicating a common crystalline structure. Here we show that the crystal structure of carmine can, at last, be determined using three-dimensional electron diffraction measurements, revealing a tetranuclear complex that assembles into a nanoporous supramolecular structure with pore diameters of approximately 1.8 nm, held together by intermolecular hydrogen bonding. Our results establish a definite structure of carmine, unveiling a surprisingly complicated arrangement in a long-used commodity with economic and cultural impact, while also highlighting the serendipitous creation of a man-made supramolecular material that dates back hundreds if not thousands of years.</p><p >The crystal structure of carmine, a long-used pigment made from dried cochineal, is unveiled through three-dimensional electron diffraction measurements. The results establish a definite structure of carmine, which is comprised of a tetranuclear metal complex that assembles into a surprisingly complex hydrogen-bonded nanoporous structure.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 12","pages":"4100–4105 4100–4105"},"PeriodicalIF":3.2,"publicationDate":"2025-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.cgd.5c00185","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144306050","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Polymorph Screening and Investigation of Charge Transport of ditBuC6-BTBT","authors":"Priya Pandey,&nbsp;Federico Modesti,&nbsp;Nemo McIntosh,&nbsp;Christian Ruzié,&nbsp;Nicholas Turetta,&nbsp;Lamiaa Fijahi,&nbsp;Massimiliano Remigio,&nbsp;Guillaume Schweicher,&nbsp;Yves Henri Geerts,&nbsp;Marta Mas-Torrent,&nbsp;Peter Erk,&nbsp;Jérôme Cornil,&nbsp;Paolo Samorì,&nbsp;Enrico Modena* and Lucia Maini*,&nbsp;","doi":"10.1021/acs.cgd.5c0004610.1021/acs.cgd.5c00046","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00046https://doi.org/10.1021/acs.cgd.5c00046","url":null,"abstract":"<p >In this study, we investigate the relationship between the polymorphism and crystallographic parameters and the charge transport properties achieved through the fabrication of organic field-effect transistors (OFETs) based on a novel molecular semiconductor, i.e., 2,7-bis(7,7-dimethyloctyl)benzo[<i>b</i>]benzo[4,5]thieno[2,3-<i>d</i>]thiophene (ditBuC6-BTBT). Four polymorphs of ditBuC6-BTBT were identified: three observed at room temperature (Forms I, Ia, and II), and one appearing above 100 °C (Form III). While cell parameters were measured for all forms, full crystal structures were determined only for Forms Ia and II. Although a direct correlation between molecular packing and charge transport properties could not be established from the present study, the structural analysis of the polymorphs contributes to a broader understanding of the packing motifs in ditBuC6-BTBT. A meticulous examination of the minute discrepancies in the powder patterns substantiated the existence of both the metastable Form I and Form Ia, which became more difficult to isolate due to unintentional seeding of the thermodynamically stable Form II. Nonequilibrium crystallization techniques utilizing thermal gradient and bar-assisted meniscus shearing methods were explored to enhance control over polymorph selection. The intrinsic charge transport properties ruled by the overlap of the frontier orbitals were studied by computing the transfer integrals. Optimized devices fabricated by depositing thin films by solution shearing and vacuum evaporation led to field-effect mobility in the linear regime of ca. 0.05 cm² V^–1 s^–1. The observed device performances were interpreted as a result of the combined effects of crystal packing features, ionization potential values, and polymorphic coexistence, highlighting the challenges in deriving clear structure–property correlations and underscoring the complexities in achieving high-performance organic electronics with this material.</p><p >Polymorph screening and OFET fabrication of a novel BTBT derivative (ditBuC6-BTBT) reveal how molecular design and polymorphic control impact charge transport in organic semiconductors.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 12","pages":"4214–4229 4214–4229"},"PeriodicalIF":3.2,"publicationDate":"2025-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.cgd.5c00046","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144305743","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Optimized Flux Single-Crystal Growth of the Quantum Spin Liquid Candidate NdTa7O19 and Other Rare-Earth Heptatantalates, ErTa7O19 and GdTa7O19","authors":"Lia Šibav,&nbsp;Matic Lozinšek,&nbsp;Zvonko Jagličić,&nbsp;Tina Arh,&nbsp;Panchanana Khuntia,&nbsp;Andrej Zorko and Mirela Dragomir*,&nbsp;","doi":"10.1021/acs.cgd.5c0062410.1021/acs.cgd.5c00624","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00624https://doi.org/10.1021/acs.cgd.5c00624","url":null,"abstract":"<p >Single crystals are essential for characterizing a wide range of magnetic states, including exotic ones such as quantum spin liquids. This study reports a flux method for growing single crystals of NdTa₇O₁₉, the first quantum spin liquid candidate on a triangular spin-lattice with dominant Ising-like spin correlations. Purple NdTa₇O₁₉ single crystals with hexagonal morphology were successfully grown by using a K₂Mo₃O₁₀–B₂O₃ flux. With lateral sizes up to 3.5 mm and a thickness up to 2 mm, these are the largest dimensions reported to date. The chemical composition was confirmed by powder and single-crystal X-ray diffraction along with scanning electron microscopy with energy dispersive X-ray spectroscopy. Aiming for an accurate determination of the magnetic anisotropy and its effect on the magnetic properties, NdTa₇O₁₉ crystals were additionally analyzed by magnetic susceptibility, revealing a substantial anisotropy without long-range magnetic ordering down to 2 K. Single crystals of two novel rare-earth heptatantalates, ErTa₇O₁₉ and GdTa₇O₁₉, were also grown, and their magnetic properties investigated. The magnetic anisotropy of ErTa₇O₁₉ closely resembles that of isostructural NdTa₇O₁₉, indicating the possibility of a similar exotic magnetic ground state. In contrast, GdTa₇O₁₉ shows paramagnetic behavior, consistent with previous results obtained for polycrystalline samples.</p><p >High-quality, large single crystals of NdTa₇O₁₉, an Ising quantum spin liquid candidate on a triangular lattice, were grown using a K₂Mo₃O₁₀–B₂O₃ flux. Magnetic susceptibility measurements down to 2 K reveal strong easy-axis anisotropy without long-range order. The flux method was also extended to grow single crystals of other rare-earth heptatantalates, ErTa₇O₁₉ and GdTa₇O₁₉.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 12","pages":"4646–4654 4646–4654"},"PeriodicalIF":3.2,"publicationDate":"2025-06-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.cgd.5c00624","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144306046","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}