Crystal Growth & Design最新文献

{"title":"Novel Piezoelectric Organic–Inorganic Hybrid Perovskite Realized by H/Cl-Substitution: [(C8H11NOCl)(18-crown-6)][FeCl4]","authors":"Xuan Qiao,&nbsp;Jian Cao,&nbsp;Feifei Xue,&nbsp;Minli Tao* and Bin Xue*,&nbsp;","doi":"10.1021/acs.cgd.4c0145310.1021/acs.cgd.4c01453","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01453https://doi.org/10.1021/acs.cgd.4c01453","url":null,"abstract":"<p >Organic–inorganic hybrid perovskites, known for their piezoelectric and ferroelectric properties, are widely used in data storage, solar cells, and molecular switches. This study introduces a novel hybrid perovskite, [(C₈H₁₁NOCl)(18-crown-6)][FeCl₄], synthesized using an H/Cl-substitution strategy to enhance its functional properties. The physical properties of the perovskite such as phase transition, dielectricity, and piezoelectric properties, were investigated based on its single-crystal and thin-film morphologies. The compound undergoes a reversible phase transition and exhibits dielectric properties, demonstrating a high Curie temperature (<i>T</i>_c = 442 K). In addition, it crystallizes in the noncentrosymmetric <i>P</i>2₁2₁2₁ space group with a unit-cell parameter of <i>a</i> = 11.8790(8) Å, <i>b</i> = 13.7901(9) Å, <i>c</i> = 18.1477(12) Å, α = β = γ = 90°, <i>Z</i> = 4, and <i>V</i> = 2972.8(3) ų. According to the results of piezoresponse force microscopy, the compound exhibits piezoelectric properties with a maximum amplitude of 370 pm in the butterfly loop. The piezoelectric properties of the compound are related to the noncentrosymmetric structure realized by H/Cl-substitution. This study not only highlights the enhanced dielectric and piezoelectric performance of the novel perovskite but also proposes a potential piezoelectric mechanism, paving the way for future design and optimization of high-performance functional materials.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 8","pages":"2367–2375 2367–2375"},"PeriodicalIF":3.2,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143832634","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":"Quantum Emitters in Flux Grown hBN","authors":"Evan Williams,&nbsp;Angus Gale*,&nbsp;Jake Horder,&nbsp;Dominic Scognamiglio,&nbsp;Milos Toth and Igor Aharonovich,&nbsp;","doi":"10.1021/acs.cgd.4c0171310.1021/acs.cgd.4c01713","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01713https://doi.org/10.1021/acs.cgd.4c01713","url":null,"abstract":"<p >Hexagonal boron nitride (hBN) is an emerging material for use in quantum technologies, hosting bright and stable single photon emitters (SPEs). The B-center is one promising SPE in hBN, due to the near-deterministic creation methods and regular emission wavelength. However, incorporation of B-centers in high-quality crystals remains challenging, typically relying on additional postgrowth methods to increase creation efficiency. Here, we have demonstrated controlled carbon doping of hBN during growth, using a metal flux-based method to increase the efficiency of B-center creation. Importantly, single B-centers with <i>g</i>⁽²⁾(0) &lt; 0.5 were able to be generated in the as-grown hBN when carbon additions during growth exceeded 2.5 wt % C. Resonant excitation measurements revealed line widths of 3.5 GHz with only moderate spectral diffusion present, demonstrating the applicability of the as-grown hBN as a host for high-quality B-centers.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 7","pages":"2083–2089 2083–2089"},"PeriodicalIF":3.2,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143745931","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":"Elastic Properties of Dichloro- and Dibromoanthracene Crystals","authors":"Yuxuan Zhao,&nbsp;Norihisa Hoshino,&nbsp;Keigo Yano,&nbsp;Shotaro Hayashi* and Tomoyuki Akutagawa*,&nbsp;","doi":"10.1021/acs.cgd.4c0103510.1021/acs.cgd.4c01035","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01035https://doi.org/10.1021/acs.cgd.4c01035","url":null,"abstract":"<p >The elastic properties of organic semiconducting crystals have attracted much attention in terms of the creation of nanomechanical devices. Dichloroanthracene (<b>Cl</b>_<b>2</b><b>An</b>) and dibromoanthracene (<b>Br</b>_<b>2</b><b>An</b>) derivatives, which form plate-like single-crystals, change the morphology of the one-dimensional (1D) column structure of anthracene and its intermolecular interaction depending on the substitution position of Cl or Br atoms. If uniform two-dimensional (2D) shear planes exist in the crystals, then the application of external stress is expected to allow elastic deformation of the crystals. However, the elastic behavior varied, depending on the morphology of the 1D column structure. Elastic behavior of the crystals was not observed when the long-axis of anthracene molecules in the π-stack tilted at 45° to each other (9,10-<b>αCl</b>_<b>2</b><b>An</b>) and when a permanent dipole moment existed at the perpendicular to the column (1,8-<b>Br</b>_<b>2</b><b>An</b>). Depending on the 1D column arrangement, elastic deformation may occur in two planes of the crystal (in the width <b><i>W</i></b> and height <b><i>H</i></b> directions of the platelet single-crystal) or only in one plane (in the height <b><i>H</i></b> direction). This can be distinguished by whether the 1D column arrangement is uniform and forms a uniform 2D-shear plane, or whether the columns are arranged in a zigzag manner, forming a 2D plane.</p><p >Elastic behaviors of dichloroanthracene and dibromoanthracene derivatives were dominated by the morphology of the one-dimensional column structure of anthracene and its intermolecular interaction depending on the substitution position of Cl or Br atoms.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 7","pages":"1952–1960 1952–1960"},"PeriodicalIF":3.2,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.cgd.4c01035","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143745807","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":"Visible-Light-Driven Deformation Triggered by [2 + 2] Cycloaddition Reactions within Isostructural Molecular Crystals","authors":"Shi Tang,&nbsp;Jiawei Lin,&nbsp;Jianmin Zhou,&nbsp;Chenyang Zhao,&nbsp;Yanbo Liu,&nbsp;Kangli Li*,&nbsp;Songgu Wu* and Junbo Gong,&nbsp;","doi":"10.1021/acs.cgd.5c0015410.1021/acs.cgd.5c00154","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00154https://doi.org/10.1021/acs.cgd.5c00154","url":null,"abstract":"<p >Photoresponsive molecular crystals with superior precise control and remote operation are considered the preferred candidates for smart materials. However, conventional photoresponsive crystals typically require high-energy and biologically damaging ultraviolet light for activation. Herein, we report three visible-light-responsive isostructural molecular crystals of cyano-styrene derivatives (DOPA-F, DOPA-Cl, and DOPA-Br) based on the [2 + 2] cycloaddition reaction. These crystals exhibit unique reactivities and macroscopically dynamic behaviors, attributed to distinct reaction pathways resulting from subtle differences in the hierarchical structure of the π-dimers. Here, the π-dimer refers to the interacting molecular pairs involved in photodimerization. Specifically, DOPA-F crystals exhibit rapid helical twisting and bending under irradiation, while DOPA-Cl and DOPA-Br bend away from the light. Moreover, DOPA-F undergoes a structural reorganization from one crystalline state to another, in contrast to DOPA-Cl and DOPA-Br, which transform from a crystalline state to an amorphous form. This work constructs eco-friendly photoresponsive materials and highlights the significant impact of subtle variations in hierarchical architecture on controlling reaction dynamics, pathways, and macroscopically dynamic behaviors.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 7","pages":"2206–2214 2206–2214"},"PeriodicalIF":3.2,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143745809","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":"Crystallographic Evidence for Formation of M6O8/M6O9 f-Element Clusters in Hydrolysis Reactions","authors":"Ethan A. Hiti,&nbsp;Geetha Bolla and Robin D. Rogers*,&nbsp;","doi":"10.1021/acs.cgd.5c0014110.1021/acs.cgd.5c00141","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00141https://doi.org/10.1021/acs.cgd.5c00141","url":null,"abstract":"<p >Understanding the formation of f-block element colloids via hydrolysis reactions, which form actinide oxo clusters, has implications in the nuclear fuel cycle, especially in high-level radioactive nuclear waste storage management. Recently, the chemistry of these species has gained attention in the development of new nuclear waste remediation technologies due to the fact that oxo and oxo–hydroxo clusters are prominent structural models for the actinides. In this contribution, we have conducted an examination of crystallographic data which includes 184 4f- and 5f-structures containing the M₆O₈ or M₆O₉ moiety. Since much of the work in this field has actually been done to explore the formation and properties of metal organic frameworks (MOFs), we hope that this collection can be used by actinide scientists to further investigate structural and mechanistic trends and gain insight into the formation of these compounds. Here we discuss the general trends in coordination, ligands used, and bonding within the M₆O₈ or M₆O₉ core in the hope that further computational work can benefit. We recognize, however, that the available crystallographic data needs a lot of improvement. In addition, use of crystallographic software (e.g., SQUEEZE) to essentially hide the rather smeared out electron density in the refinement can improve the crystallographic refinement parameters obtained, but it leads to a lot of possible interpretations of the overall structure, including charge balance. This does not bode well for predicting the exact phases which may solidify from complex nuclear waste with a variety of anions and decomposition products present, and much more study using advanced analytical techniques beyond crystallography is warranted.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 7","pages":"2267–2324 2267–2324"},"PeriodicalIF":3.2,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143745801","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":"Controllable Syntheses of a Two-Dimensional Coordination Framework and Its Discrete Heteroleptic Building Blocks","authors":"Thanh Nhan Nguyen,&nbsp;Anh Ngoc Nguyen,&nbsp;Thang Cao Doan,&nbsp;Taehun Kim,&nbsp;Eunji Lee,&nbsp;In-Hyeok Park* and Hyojong Yoo*,&nbsp;","doi":"10.1021/acs.cgd.5c0013310.1021/acs.cgd.5c00133","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00133https://doi.org/10.1021/acs.cgd.5c00133","url":null,"abstract":"<p >Controllable syntheses of a two-dimensional (2D) coordination polymer and its discrete triple-stranded helicate (TSH) building units using a solvent-assisted approach are reported. In a single TSH, two multinuclear nickel clusters, each assembled from four nickel ions and three 2,6-pyridinedicarboxylates, are interconnected by three V-shaped 4,4′-pyridine-2,6-diyldibenzoate (PDDB) bridging ligands. The long distance between two terminal carboxyl groups, together with the bending angle of 120° in the PDDB, generates a void inside the TSH, which is functionalized by the pyridinic ring at the center of PDDBs. Dimethylammonium ions, which are present in the solid state of discrete TSHs, neutralize the charge of TSHs and stabilize the solid structure with hydrogen bonding. Large-sized TSHs possess high connectivity and proper symmetry for constructing a 2D hierarchical coordination framework, which is a rare coordination platform obtained using the supermolecular building block (SBB) approach. The conversion of discrete TSHs into a 2D framework illustrates the suitability of discrete TSHs as SBBs for constructing higher-order coordination-driven frameworks.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 7","pages":"2186–2192 2186–2192"},"PeriodicalIF":3.2,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143746163","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":"FOX-7-Fused Bicyclic Guanidinium Salts: A Series of High-Density Insensitive Energetic Materials","authors":"Pengxiang Gao,&nbsp;Bin Song,&nbsp;Pengfei Wang,&nbsp;Bingcheng Hu and Chong Zhang*,&nbsp;","doi":"10.1021/acs.cgd.4c0117110.1021/acs.cgd.4c01171","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01171https://doi.org/10.1021/acs.cgd.4c01171","url":null,"abstract":"<p >Polycyclic nitrogen-rich energetic compounds have attracted the attention of domestic and foreign researchers due to their unique advantages in constructing low mechanical sensitivity, good thermal stability, and high-density new energetic molecules. In this study, a series of nitrogen-rich polycyclic energetic ion salts were synthesized. The resulting compounds were structurally characterized and thermally analyzed, and their detonation properties were calculated using <i>EXPLO5</i> software in combination with the enthalpy of generation calculated by Gaussian 09 software. Among them, compound <b>3</b> (ρ = 1.881 g cm^–3, IS = 30 J, and FS = 252 N) demonstrates the best detonation performance, which is better than RDX, with <i>p</i> = 35.48 GPa, <i>D</i> = 8920 m·s^–1, and is expected to be an alternative to conventional explosives. The results of this study suggest that the combination of nitrogen-rich fused rings and energetic units (nitro et al.) will be a promising direction for the design of new high-energy-density materials in the future.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 7","pages":"1961–1968 1961–1968"},"PeriodicalIF":3.2,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143746161","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":"Unraveling the Correlation between Crystal Orientation and Thickness Uniformity of Wafer-Scale AlN Films","authors":"Zhengwang Cheng*,&nbsp;Huating Bo,&nbsp;Qixing Wang,&nbsp;Jiajun Liao,&nbsp;Aobo Wang,&nbsp;Shengjia Li,&nbsp;Fan Sheng,&nbsp;Wei Zou,&nbsp;Mei Wang* and Xinguo Ma*,&nbsp;","doi":"10.1021/acs.cgd.4c0137010.1021/acs.cgd.4c01370","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01370https://doi.org/10.1021/acs.cgd.4c01370","url":null,"abstract":"<p >Preparing piezoelectric AlN films with a high thickness uniformity at the wafer scale is important for improving the device performance and reducing the manufacturing cost. Here, we deposit sets of AlN films onto Si(100) wafers through the direct-current (DC) magnetron sputtering (MS) method under diversified process parameters, including sputtering power, Ar/N₂ gas flow ratio, pressure, substrate temperature, and target–substrate distance. The impact trends of each parameter on the thickness nonuniformity are systematically studied. Furthermore, the relationship between crystal orientation and thickness uniformity of AlN films was unraveled by combining experimental and theoretical investigations. We find that the coexistence of (100) and (002) planes is favorable for the preparation of uniform AlN films and reaches the minimum thickness nonuniformity of 0.596% when the (100)/(002) XRD peak ratio is close to 0.77. Besides, the ultrauniform AlN films show high crystallinity (0.16° for the FWHM of XRD peaks) and an outstanding piezoelectric performance (d₃₃ = 34 pm/V). Our findings not only uncover the correlation between crystal orientation and thickness uniformity of AlN films, but also provide a reference for the deposition of other uniform films.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 7","pages":"1969–1977 1969–1977"},"PeriodicalIF":3.2,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143746162","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":"Cu-Based Metal–Organic Frameworks Characterized by V-Shaped Ligands and Application to Efficient Separation of C2H2/CO2 and C2H2/CH4","authors":"Miaomiao Zhang,&nbsp;Jiashuo Zhao,&nbsp;Siqi Li,&nbsp;Xiaolong Luo*,&nbsp;Shi-Tong Zhang,&nbsp;Yizhi Shao* and Xiaofei Zhu*,&nbsp;","doi":"10.1021/acs.cgd.4c0152410.1021/acs.cgd.4c01524","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01524https://doi.org/10.1021/acs.cgd.4c01524","url":null,"abstract":"<p >Two Cu-based metal–organic frameworks (Cu-MOFs) with new topologies were successfully synthesized under solvothermal conditions using V-shaped nitrogen-containing tetracarboxylic acid ligands: [Cu₉O(PADDA)₄(H₂O)₆]·xGuest (compound <b>1</b>), [H₃O][Cu₆(PIDDA)₃(H₂O)₄(HCOO)]·xGuest (compound <b>2</b>), (H₄PADDA = 5,5′-(pyrazine-2,6-diyl)diisophthalic acid; H₄PIDDA = 5,5′-(pyrimidine-4,6-diyl)diisophthalic acid). Structural analysis reveals that both compounds are constructed from [Cu₂(COO)₄] characterized by classic paddlewheel building units. Notably, compound <b>1</b> features a rare structural unit of tetranuclear copper characterized by two paddlewheel-structured dinuclear copper units connected by a bridging oxygen atom. In contrast, compound <b>2</b> features a structural unit of tetranuclear copper formed by formic acid connecting two adjacent paddlewheel-structured dinuclear copper units. Both frameworks exhibit three distinct cage structures of different sizes. These compounds demonstrate high specific surface areas and excellent adsorption capabilities for small gas molecules, such as CO₂, CH₄, and C₂H₂, enabling effective purification of acetylene. At 100 kPa and 298 K, compound <b>1</b> show an ideal adsorbed solution theory (IAST) selectivity of 4.0 and 20.0 for equimolar C₂H₂/CO₂ and C₂H₂/CH₄ mixtures, respectively. The IAST selectivity corresponding to compound <b>2</b> increased to 7.1 and 57.6. Meanwhile, the actual separation performance was verified by breakthrough experiments, demonstrating the potential to separate C₂H₂/CO₂ and C₂H₂/CH₄ mixtures at room temperature.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 7","pages":"2002–2012 2002–2012"},"PeriodicalIF":3.2,"publicationDate":"2025-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143746155","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":"Special Issue: Honoring Professor Jagadese J. Vittal and His Contributions to Functional Molecular Crystals","authors":"Goutam Kumar Kole*,&nbsp;Raghavender Medishetty*,&nbsp;Mohammad Hedayetullah Mir*,&nbsp;Jan Kazimierz Zaręba,&nbsp;Miki Hasegawa,&nbsp;Leonard R. MacGillivray,&nbsp;Sanjit Konar and Jonathan W. Steed,&nbsp;","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}