Crystal Growth & Design最新文献

{"title":"Special Issue: Honoring Professor Jagadese J. Vittal and His Contributions to Functional Molecular Crystals","authors":"Goutam Kumar Kole*, Raghavender Medishetty*, Mohammad Hedayetullah Mir*, Jan Kazimierz Zaręba, Miki Hasegawa, Leonard R. MacGillivray, Sanjit Konar and Jonathan W. Steed, ","doi":"10.1021/acs.cgd.4c0172810.1021/acs.cgd.4c01728","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01728https://doi.org/10.1021/acs.cgd.4c01728","url":null,"abstract":"","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 7","pages":"1949–1951 1949–1951"},"PeriodicalIF":3.2,"publicationDate":"2025-03-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143746043","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":"Lanthanide-Based Single-Molecule Magnets Derived from Lacunary Polyoxometalates","authors":"Kenta Hirakawa,&nbsp;Yoshihiro Sekine,&nbsp;Fumiya Kobayashi,&nbsp;Yoji Horii,&nbsp;Hikaru Zenno,&nbsp;Manabu Nakaya and Shinya Hayami*,&nbsp;","doi":"10.1021/acs.cgd.5c0011110.1021/acs.cgd.5c00111","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00111https://doi.org/10.1021/acs.cgd.5c00111","url":null,"abstract":"<p >Toward the development of new functional materials with single-molecule magnet (SMM) behavior, novel lacunary Dawson-type polyoxometalate (POM)-based clusters containing lanthanide ions (Dy³⁺ and Tb³⁺) were synthesized and their applicability as SMMs was verified. Four discrete complexes were obtained at a mixing ratio of lanthanide ions to lacunary POM clusters of 2:2 or 1:2, yielding K₁₄[Dy₂(P₂W₁₇O₆₁)₂]·52H₂O (<b>1</b>), K₁₇[Dy(P₂W₁₇O₆₁)₂]·52H₂O (<b>2</b>), K₁₄[Tb₂(P₂W₁₇O₆₁)₂]·52H₂O (<b>3</b>), and K₁₇[Tb(P₂W₁₇O₆₁)₂]·53H₂O (<b>4</b>), which were characterized by single-crystal X-ray structural analysis. Detailed measurements of the alternating current (ac) magnetic properties revealed that <b>1</b> and <b>2</b> exhibited the SMM behavior (<i>U</i>_eff/<i>k</i>_B = 2.19 and 22.23 K, τ₀ = 9.02 × 10^–7 and 4.56 × 10^–5 s, <i>H</i>_dc = 3000 and 1000 Oe, respectively), unlike <b>3</b> and <b>4</b>. The distorted geometry of Dy³⁺ ions in <b>2</b> in relation to that in <b>1</b> resulted in slow magnetic relaxation caused by SMMs with larger energy barrier values, according to temperature-dependent ac susceptibility measurements and theoretical calculations. Therefore, new hybrid materials as SMMs from trivalent lanthanide ions and lacunary POM clusters can be fabricated. This study opens new avenues for constructing next-generation compounds that exhibit interesting slow magnetic relaxation based on the assembly of lanthanide ions and lacunary POMs.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 7","pages":"2163–2171 2163–2171"},"PeriodicalIF":3.2,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143746040","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":"Axial Carbonate-Bridged Dy2 Complexes Having Rigid N3O2 Equatorial Planes: Stepwise Boosting and Tuning of the Zero-Field SMM Behavior","authors":"Naushad Ahmed*,&nbsp; and ,&nbsp;Donald J. Darensbourg*,&nbsp;","doi":"10.1021/acs.cgd.4c0146810.1021/acs.cgd.4c01468","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01468https://doi.org/10.1021/acs.cgd.4c01468","url":null,"abstract":"<p >Herein, we report the synthesis of carbonate-bridged binuclear Ln(III) complexes [Dy₂(<b>L</b>_<b>1</b>^2–)₂(CO₃^2–)(MeOH)₂] complex <b>1-Dy</b>_<b>2</b>, [Y₂(<b>L</b>_<b>1</b>^2–)₂(CO₃^2–)(MeOH)₂] complex <b>1-Y</b>_<b>2</b>, [Dy₂(<b>L</b>_<b>1</b>^2–)₂(CO₃^2-)(MeOH)(TPPO)] complex <b>2-Dy</b>_<b>2</b>, [Y₂(<b>L</b>_<b>1</b>^2–)₂(CO₃^2–)(MeOH)(TPPO)] complex <b>2-Y</b>_<b>2</b>, [Dy₂(<b>L</b>_<b>1</b>^2–)₂(CO₃^2–)(TPPO)₂] complex <b>3-Dy</b>_<b>2</b>, and [Dy₂(<b>H</b>_<b>2</b><b>L</b>_<b>2</b>^2–)₂(CO₃^2–)(TPPO)₂] complex <b>4-Dy</b>_<b>2</b>, having a rigid equatorial pentagonal plane around each Ln(III) ion. The Schiff base <b>H</b>_<b>2</b><b>L</b>_<b>1</b> (2,6-diacetylpyridine bis-benzoyl hydrazone) and <b>H</b>_<b>4</b><b>L</b>_<b>2</b> (2,6-diacetylpyridine bis-salicyl hydrazone) ligands were used to provide a rigid equatorial pentagonal plane to the Ln(III) ions through their N₃O₂ donor atoms. One of the axial sites of each Ln(III) is occupied by triphenylphosphine oxide (TPPO) or methanol ligand, while CO₃^2– occupies the other axial sites. The successful replacement of axially coordinated methanol by the TPPO ligand boosted the zero-field SMM property in <b>3-Dy</b>_<b>2</b>. We observed that phenolic −OH in <b>H</b>_<b>2</b><b>L</b>_<b>2</b>^2– ligands imposes significant structure orientation in <b>4-Dy</b>_<b>2</b> compared to <b>3-Dy</b>_<b>2</b> and tunes the zero-field SMM properties by altering the Dy1-<i>O</i>-Dy2 bridging angle.</p><p >We have synthesized axial carbonate-bridged Dy₂ complexes with N₃O₂ rigid equatorial planes and demonstrated the stepwise boosting and diminishing of the zero-field SMM behavior by replacing axial ligands and altering the bridging angle.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 7","pages":"1992–2001 1992–2001"},"PeriodicalIF":3.2,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.cgd.4c01468","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143746041","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":"Various Methods of Synthesis and Applications of Gold-Based Nanomaterials: A Detailed Review","authors":"Misbah Gul,&nbsp;Muhammad Kashif,&nbsp;Sheraz Muhammad,&nbsp;Shohreh Azizi* and Hao Sun*,&nbsp;","doi":"10.1021/acs.cgd.4c0168710.1021/acs.cgd.4c01687","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01687https://doi.org/10.1021/acs.cgd.4c01687","url":null,"abstract":"<p >Gold-based nanoparticles (Au NPs) have emerged as essential materials in nanotechnology due to their unique optical, electronic, and catalytic properties. This Review explores the synthesis, functionalization, and broad spectrum of applications of Au NPs. Key synthesis methodologies, such as chemical reduction and green synthesis, are discussed with a focus on how they influence nanoparticle size, shape, and stability. Surface functionalization techniques that enhance biocompatibility and target specificity are examined in detail. The versatile applications of Au NPs in biomedicine, ranging from diagnostic imaging and targeted drug delivery to cancer therapy through hyperthermia, underscore their utility in modern healthcare. Furthermore, Au NPs’ superior conductivity and manufacturability drive innovations in electronic applications, including sensors, conductive inks, and nanoelectronics for next-generation devices. In environmental science, their efficacy in detecting pollutants and purifying water is highlighted, representing a promising avenue for ecological applications. Collectively, these applications demonstrate the dynamic role of gold-based nanoparticles across multiple fields, emphasizing the need for continued research and innovations to harness their potential and address current challenges.</p><p >This Review provides an in-depth exploration of gold-based nanoparticles (Au NPs), focusing on their synthesis, functionalization, and wide range of applications. It highlights key synthesis methods, including chemical reduction and green synthesis, and their impact on nanoparticle properties such as size, shape, and stability. The Review also examines the diverse applications of Au NPs in photocatalysis, biomedicine, electronics, and environmental science, underscoring their importance and the need for ongoing research to unlock their full potential.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 7","pages":"2227–2266 2227–2266"},"PeriodicalIF":3.2,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.cgd.4c01687","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143746024","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":"Zeolitic Metal–Organic Framework with High-Density Hydrophilic Sites for Efficient Proton Conduction","authors":"Ping Li,&nbsp;Junchao Dong,&nbsp;Hao Zhang,&nbsp;Jialu Li*,&nbsp;Jiyang Li,&nbsp;Jia Liu*,&nbsp;Fanyu Meng* and Xiaoqin Zou*,&nbsp;","doi":"10.1021/acs.cgd.5c0008110.1021/acs.cgd.5c00081","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00081https://doi.org/10.1021/acs.cgd.5c00081","url":null,"abstract":"<p >Proton exchange membranes play a key role in fuel cells; however, the development of highly proton-conductive and stable materials still remains a challenge. Herein, a hydrolysis coordination strategy was proposed for the synthesis of a three-dimensional porous metal–organic framework (MOF) [Zn₈Na₄(ImDC)₁₂]. This MOF was structured with an ACO zeolite topology and high-density hydrophilic sites of nitrogen and oxygen. Under high-temperature and humidity conditions (353 K, 76% RH), [Zn₈Na₄(ImDC)₁₂] exhibited proton conductivity as high as 0.016 S cm^–1, outperforming that of most MOF materials reported previously. Mixed-matrix membranes of [Zn₈Na₄(ImDC)₁₂]@CS were fabricated with [Zn₈Na₄(ImDC)₁₂] and a chitosan polymer. The membrane with 10 wt % [Zn₈Na₄(ImDC)₁₂] showed an optimal proton conductivity of 0.051 S cm^–1. This study provides guidance for developing high-performance proton conduction materials.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 7","pages":"2155–2162 2155–2162"},"PeriodicalIF":3.2,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143746042","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":"Monocation vs Dication 2D → 1D Dimensional Reduction Agent Affording Broad Band Emitters 1D Lead Bromide Perovskites","authors":"Maria Maniadi,&nbsp;Nicolas Mercier*,&nbsp;Chiara Botta,&nbsp;Valérie Dupray and Alexandre Abhervé,&nbsp;","doi":"10.1021/acs.cgd.5c0003010.1021/acs.cgd.5c00030","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00030https://doi.org/10.1021/acs.cgd.5c00030","url":null,"abstract":"<p >The synthesis, crystal structures, and optical properties of the 2D perovskite (Cyst)PbBr₄ (<b>1</b>) and two 1D perovskite hybrids Cs(Cyst)PbBr₅ (<b>2</b>) and (Cyst)₂PbBr₅,Br (<b>3</b>) based on the cystaminium dication (Cyst²⁺) exhibiting a helical chiral conformation are described in this work. The 1D compounds can be conceptually described from the 2D mother structure by the dimensional reduction concept. Thus, the addition of one CsBr unit to one (Cyst)PbBr₄ leads to Cs(Cyst)PbBr₅ (<b>2</b>), whose structure can be described as organic–inorganic sheets [(Cyst)PbBr₅]⁻ separated by Cs⁺ monocation in the intersheet space, while the addition of one (Cyst),2Br unit to one (Cyst)PbBr₄ leads to (Cyst)₂PbBr₅,Br (<b>3</b>) whose structure can be described as organic–inorganic sheets [(Cyst)PbBr₅]⁻ separated by Cyst²⁺ dications and free bromides in the intersheet space. The acentric compound (<b>2</b>) crystallizing in the <i>P</i>2₁ space group exhibits SHG properties, while the three compounds emit light when excited in the UV–visible domain. The 2D compound exhibits two close excitonic narrow peaks in the blue region, certainly resulting from bulk and edge states as already observed. In contrast, the lower-dimensional compounds (<b>2</b>) and (<b>3</b>) have a broad band emission type covering a good part of the visible range, illustrating the interest of such low-dimensional 1D compounds compared to 2D mother compounds for white light type emission.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 7","pages":"2128–2134 2128–2134"},"PeriodicalIF":3.2,"publicationDate":"2025-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143746060","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":"Cocrystallization of Progesterone with Benzoic Acid and Its Derivatives","authors":"Juan Xu,&nbsp;XiaoFeng Chen and LiFeng Ning*,&nbsp;","doi":"10.1021/acs.cgd.4c0152010.1021/acs.cgd.4c01520","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01520https://doi.org/10.1021/acs.cgd.4c01520","url":null,"abstract":"<p >Thirty three cocrystals and cocrystal solvates of progesterone (PRO) with benzoic acid and its derivatives were prepared under solvent-free grinding conditions. Twenty five cocrystals and cocrystal solvates were reported for the first time, of which 15 cocrystals and cocrystal solvates had single crystal data (CCDC deposition numbers 2131358–2131360, 2131363, 2131364, 2131366–2131373, 2131376, and 2131377). For cocrystal formers (CCF), the carboxyl group attached directly to the aromatic ring had a role similar to that of the orientation effect. The cocrystallization between PRO and benzoic acid or substituted benzoic acids was highly likely to take place regardless of the presence of electron-withdrawing or electron-donating groups in the <i>o</i>-, <i>m</i>-, <i>p</i>-position of the carboxyl group. When CCFs were hydrogen-bonded to PRO, they bonded to the carbonyl group on ring “A” of PRO first and then to the carbonyl group attached to ring “D”. The calculation results of the electrostatic potential maximum value confirmed this conclusion. Quantum chemical calculations of PRO/benzoic acid/H₂O (4:2:1) showed that the most important force in this system was the C–H···π among PRO-benzoic acid-PRO. All cocrystals and cocrystal solvates were more soluble than PRO in water. The preparation of cocrystals is an effective attempt to design a new PRO administration method.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 7","pages":"2013–2019 2013–2019"},"PeriodicalIF":3.2,"publicationDate":"2025-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143746058","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":"Solvent Entrapment of BI 763963 by Solid Solution Formation","authors":"Samruddhi Patil,&nbsp;Tao Zhang,&nbsp;Brian Linehan,&nbsp;Vincent Abeyta and Fredrik L. Nordstrom*,&nbsp;","doi":"10.1021/acs.cgd.5c0005010.1021/acs.cgd.5c00050","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00050https://doi.org/10.1021/acs.cgd.5c00050","url":null,"abstract":"<p >The underlying mechanism for solvent entrapment has been determined for terminated drug candidate BI 763963. Ethanol (EtOH) and isopropanol (IPA) were entrapped in the crystal lattice of BI 763963 through solid solution formation, as demonstrated through a combination of experimental methods and structural analysis. Two binary T-w phase diagrams were constructed showing the outline of the solidus and liquidus, where EtOH and IPA are present in the solid phase of BI 763963 at 0.54 and 1.5 wt %, respectively, at equilibrium. Importantly, the solvent solubility of BI 763963 was found to be dependent on the residual solvent level in the solid phase and in the case of EtOH increased by almost 50% at just 1.1 wt % EtOH entrapment. The implications of the effect of residual solvents on solvent solubility are discussed with respect to industrial processing and the pharmaceutical properties of the active pharmaceutical ingredient (API). Furthermore, recrystallization experiments were carried out on BI 763963 at different supersaturation ratios in both EtOH and IPA. Higher supersaturation yielded higher solvent entrapment initially, which in both solvents decreased linearly with API yield. The trends are discussed and compared to previous contributions showing similar behavior that appeared due to crystal nucleation of a solid solution. The solubility-enhancing effect from solvent entrapment is used to determine the actual supersaturation ratio during crystallization. The analysis shows that errors up to 55% in the supersaturation ratio can be introduced when assuming that the solid phase is pure or that the solubility of an API is independent of entrapped solvent. Finally, industrial mitigation measures are discussed to reduce residual solvent levels based on solid solution formation. It is demonstrated experimentally that other solid-state miscible impurities can completely alter the phase equilibria of the system, leading in one example to a reduction in IPA content from 2.2 to 0.86 wt %.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 6","pages":"1897–1911 1897–1911"},"PeriodicalIF":3.2,"publicationDate":"2025-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143641399","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":"A Bis-Imidazolium Receptor for the Selective Crystallization of Fluoride through Hydrogen Bonding","authors":"Lili Jin,&nbsp;Yuntao Lei,&nbsp;Anthony Dodd,&nbsp;Peter Nockemann* and H. Q. Nimal Gunaratne*,&nbsp;","doi":"10.1021/acs.cgd.4c0153210.1021/acs.cgd.4c01532","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01532https://doi.org/10.1021/acs.cgd.4c01532","url":null,"abstract":"<p >Selective recognition and separation of fluoride anions from other halides remain significant challenges in supramolecular chemistry due to the similar physicochemical properties of halide ions and the environmental concerns associated with fluoride contamination. We report a simple dicationic bis-imidazolium receptor with hydroxyethyl pendants that selectively binds fluoride ions over other halides through a selective “bidentate” hydrogen bonding mechanism involving C2–H···F^– and O–H···F^– interactions. This unique binding mode facilitates the crystallization of a fluoride complex from polar solvents containing chloride, bromide, or iodide ions. Despite minimal preorganization, the receptor exhibits size-matched binding pockets that selectively accommodate fluoride ions, enabling their separation from equimolar halide mixtures. This work introduces a new approach to fluoride recognition and offers potential applications in environmental remediation and industrial processes.</p><p >A simple dicationic bis-imidazolium receptor selectively crystallizes fluoride over other halides from polar solvents. The receptor’s size-matched binding pockets enable selective “bidentate” C−H···F⁻ and O−H···F⁻ hydrogen bonding, offering a new approach for simplified halide discrimination and potential environmental remediation.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 6","pages":"1725–1730 1725–1730"},"PeriodicalIF":3.2,"publicationDate":"2025-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.cgd.4c01532","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143641386","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":"Single Crystal Growth of Type-II Si Clathrate Containing Fully Occupied Na and Ba from a Na-Based Metal Complex Solution","authors":"Haruhiko Morito*,&nbsp;Yutaka IIjima,&nbsp;Masaya Fujioka,&nbsp;Rodion V. Belosludov,&nbsp;Masami Terauchi,&nbsp;Hisanori Yamane and Kozo Fujiwara,&nbsp;","doi":"10.1021/acs.cgd.5c0001310.1021/acs.cgd.5c00013","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00013https://doi.org/10.1021/acs.cgd.5c00013","url":null,"abstract":"<p >Single crystals of the Na–Ba–Si ternary clathrate were grown by heating a melt consisting of Na, Ba, Si, and Sn at 823 or 873 K and evaporating Na from the melt. The single crystals grown at 873 K had triangular {111} facets, with the length of one side of the triangle reaching up to 0.8 mm for crystals grown at 873 K. Both single crystals grown at 823 and 873 K exhibited a type-II clathrate structure (cubic, <i>Fd</i>3̅<i>m</i>), specifically Na₁₆Ba_7.71Si₁₃₆ (<i>a</i> = 14.7008(3) Å) and Na_16.72Ba_7.28Si₁₃₆ (<i>a</i> = 14.7007(3) Å), as determined by X-ray crystal structure analysis. Na and Ba are encapsulated in the Si₂₀ and Si₂₈ cages of type-II clathrate structure, respectively. Metallic electrical conduction was observed for the single crystal grown at 873 K with an electrical conductivity of 0.12 × 10^–3 Ω cm at room temperature. The results of soft X-ray emission spectroscopy and the electronic density of states calculations also revealed that the Na–Ba–Si ternary clathrate with a type-II structure has a metallic electronic state.</p><p >Single crystals of a novel type-II Na−Ba−Si clathrate in which Na and Ba completely occupy the Si cages were grown from a Na-based metal complex solution.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 7","pages":"2120–2127 2120–2127"},"PeriodicalIF":3.2,"publicationDate":"2025-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.cgd.5c00013","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143745889","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}