CrystEngComm最新文献

{"title":"Influence of varying the nickel salt aqueous subphase on the formation of Ni3(hexaiminotriphenylene)2 metal–organic framework nanosheets at the air/liquid interface†","authors":"Kazuaki Tachimoto, Kanokwan Jumtee Takeno and Rie Makiura","doi":"10.1039/D5CE00630A","DOIUrl":"https://doi.org/10.1039/D5CE00630A","url":null,"abstract":"<p >Metal–organic framework (MOF) nanosheets synthesized at the air/liquid interface exhibit properties, such as electrical conductivity, that are highly dependent on their structural attributes, including morphology, lateral dimensions, thickness, crystallinity, and orientation. Achieving precise control over these features, however, remains a significant challenge. Extending our previous works on the air/liquid interfacial synthesis of uniaxially oriented Ni<small>₃</small>(HITP)<small>₂</small> nanosheets (<strong>HITP-Ni-NS</strong>), this study explores the profound influence of the metal salt counterion—a key parameter in MOF crystallization. We present a systematic investigation into how nickel acetate (Ni(OAc)<small>₂</small>), nickel chloride (NiCl<small>₂</small>), and nickel nitrate (Ni(NO<small>₃</small>)<small>₂</small>) precursors affect the resulting nanosheet morphology, thickness, crystallinity, and orientation. Our comparative interfacial syntheses demonstrate that variations in the counterion significantly impact crystal growth kinetics, leading to discernible differences in nanosheet architecture. Notably, while NiCl<small>₂</small> and Ni(NO<small>₃</small>)<small>₂</small> precursors result in the incorporation of unreacted HATP ligand stacks and subsequent nanosheet disorder, Ni(OAc)<small>₂</small> consistently produces <strong>HITP-Ni-NS</strong> with the greatest thickness and maintains perfect alignment with a preferred ordered crystalline stacking orientation. These observed differences are attributed to variations in the <strong>HITP-Ni-NS</strong> crystal growth mechanism, likely mediated by the distinct pH of the nickel aqueous subphases. These findings highlight the critical role of the metal salt counterion in directing the growth and ultimately tailoring the functional properties of MOF nanosheets.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 35","pages":" 5793-5802"},"PeriodicalIF":2.6,"publicationDate":"2025-08-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ce/d5ce00630a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145007880","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":"Controlling FOX-7 crystal morphology via the emulsion method: monodisperse micron-sized spherical aggregates and enhanced safety performance","authors":"Rui Qu, Zheng Li, Xiaofeng Guo, Yipeng Zhang, Hao Guo, Mengxuan Zheng and Changping Guo","doi":"10.1039/D5CE00620A","DOIUrl":"https://doi.org/10.1039/D5CE00620A","url":null,"abstract":"<p >The crystal morphology and particle size distribution of explosives are the decisive factors affecting their detonation characteristics and sensitivity. In this paper, the oil-in-oil emulsion method was used to study the effects of the type and amount of surfactants and the ratio of the discontinuous phase to the continuous phase on the stability of the emulsion with DMSO as the discontinuous phase and cyclohexane as the continuous phase. Spherical FOX-7 with dimensions of tens of microns was successfully prepared, which filled the technical gap in the preparation of mesoscale spherical FOX-7, and its morphology, specific surface area, fluidity, structure, thermal decomposition and safety were characterized. The results showed that the stable emulsion could be obtained when Tween-80 was selected as the surfactant, the dosage was 3 g L<small>⁻¹</small>, and the ratio of the discontinuous phase to the continuous phase was 1 : 3. The size of spherical FOX-7 was between 30–70 μm, the <em>D</em><small>₅₀</small> was 43.1 μm, the specific surface area was 1.502 m<small>²</small> g<small>⁻¹</small>, and the fluidity was greatly improved. The change of morphology did not cause the change of crystal form. Compared with the raw material FOX-7, the thermal stability of the sphere is better, and the apparent activation energy is reduced by 65.36 kJ mol<small>⁻¹</small>. The characteristic drop height (<em>H</em><small>₅₀</small>) is increased by 22.77 cm, the friction sensitivity is reduced from 20% to 8%, and the safety performance is better. This study is expected to provide new ideas for the performance optimization of high-energy insensitive explosives.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 38","pages":" 6341-6349"},"PeriodicalIF":2.6,"publicationDate":"2025-08-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145183994","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":"Coordinated water modulation for proton conductivity via post-synthetic transmetalation in yttrium-based coordination polymers","authors":"Byoung Gwan Lee, Dongwook Kim, Jin Young Bae, Ji Woo Jeong and Dae-Woon Lim","doi":"10.1039/D5CE00639B","DOIUrl":"https://doi.org/10.1039/D5CE00639B","url":null,"abstract":"<p >Understanding the correlation between structural variations and proton transport in coordination polymers (CPs) is essential for developing efficient solid-state proton conductors (SSPCs). In this study, we demonstrate that post-synthetic transmetalation <em>via</em> alkali metal exchange enhances proton conductivity in a pseudo-three-dimensional yttrium-based CP, {[Y(H<small>₂</small>O)<small>₄</small>(HDSNDC)]·H<small>₂</small>O}<small>_<em>n</em></small> (H<small>₄</small>DSNDC = 4,8-disulfonaphthalene-2,6-dicarboxylic acid). Immersion in 1 M KCl solution induces transmetalation, yielding a potassium-substituted analogue, {K<small>₃</small>(H<small>₂</small>O)<small>₂</small>(HDSNDC)}<small>_<em>n</em></small>. Structural analysis reveals that transmetalation induces structural reorganization, in which terminal H<small>₂</small>O ligands are converted into μ-bridging ones. These bridging H<small>₂</small>O ligands exhibit increased acidity due to cooperative polarization by adjacent K<small>⁺</small> ions, facilitating proton dissociation and significantly enhancing conductivity from 7.23 × 10<small>⁻⁵</small> S cm<small>⁻¹</small> for Y-DSNDC to 2.50 × 10<small>⁻³</small> S cm<small>⁻¹</small> for K-DSNDC at 363 K under 95% RH. This work highlights transmetalation-induced coordination tuning as an effective strategy to enhance proton transport in CPs.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 36","pages":" 5952-5958"},"PeriodicalIF":2.6,"publicationDate":"2025-08-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145057486","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 thermal and optical properties of Li+-modified Yb3+-doped Ca3Nb1.6875Ga3.1875O12 single crystal grown by the Bridgman method","authors":"Lintao Zhou, Linwen Jiang, Zhigang Sun and Yanqing Zheng","doi":"10.1039/D5CE00356C","DOIUrl":"https://doi.org/10.1039/D5CE00356C","url":null,"abstract":"<p >Yb<small>³⁺</small>-doped Ca<small>₃</small>Nb<small>_1.6875</small>Ga<small>_3.1875</small>O<small>₁₂</small> (Yb:CLNGG) crystals with structural disorder have widespread applications in laser fields. In this paper, we study the thermal and optical properties of Yb:CLNGG single crystals grown by the Bridgman method, as well as the structural and functional alterations induced by O<small>₂</small>-annealing and Ar-annealing treatments. The Yb:CLNGG crystals were characterized by Raman spectroscopy, X-ray photoelectron spectroscopy, transmission spectroscopy, and emission spectroscopy. The absorption cross section, emission cross section, and gain cross section of the Yb:CLNGG were calculated. The emission bandwidth of Yb:CLNGG was enhanced from 22 nm to 29 nm by annealing in the Ar environment and the luminescence lifetime was extended from 1.26 ms to 1.46 ms. The above results indicate that the performance of the Yb:CLNGG crystal is improved after annealing in Ar and it is a suitable material for ultrafast lasers.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 37","pages":" 6137-6145"},"PeriodicalIF":2.6,"publicationDate":"2025-08-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145100552","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A quantitative method for investigating 3D oxygen transport pathways in Czochralski growth of a silicon crystal","authors":"Jiancheng Li, Jinping Luo, Zeqi Zhong, Junlei Wang, Zaoyang Li, Yong Wen, Lei Wang, Hui Xu and Lijun Liu","doi":"10.1039/D5CE00686D","DOIUrl":"https://doi.org/10.1039/D5CE00686D","url":null,"abstract":"<p >Elucidating complex oxygen transport is key to precise oxygen control in Czochralski (Cz) growth of a silicon crystal. We propose a quantitative method for investigating 3D oxygen transport pathways. This method can compute the origin and destination as well as the exact shape of the oxygen transport pathways in the melt. It is realized by analogizing oxygen transport to a kind of convection transport and calculating the oxygen transport ‘velocity field’. Similar to the streamlines, the pathways are obtained by numerically integrating the ‘velocity field’. Applied to the continuous-feeding Czochralski method (CCz), the results demonstrate that the shape of the pathways is approximately spiral. The rotation direction and angle of the spiral pathway are governed by the ratio of circumferential convection flux to that of axial turbulent-diffusion, while its radius evolves with the radial to axial turbulent-diffusion flux ratio. The oxygen transport pathways to the crystallization interface originate from within a circle (named ‘circle O’) at the crucible bottom, whose radius is smaller than that of the crystal and governed by the axial variation rate of the radius along the transport pathways to the three-phase contact line. This finding enables precise control of the source of oxygen transported into the silicon. Through the quantitative analysis, we also find that the inner-crucible increases the oxygen content not because of its proximity to the crystallization interface facilitating its dissolved oxygen transport into the silicon as generally accepted, but because it expands the radius of ‘circle O’ and enhances axial turbulent-diffusion. Moreover, this method is potentially applicable to quantitative studies of impurity transport for other crystal growth processes.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 34","pages":" 5769-5778"},"PeriodicalIF":2.6,"publicationDate":"2025-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144909506","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":"Numerical simulation and modified Bridgman growth of high-quality and large-sized LiGaS2 mid-infrared optical crystals","authors":"Chao Ma, Xingguang Li, Shilei Wang, Kaihui Xu, Zerui Li, Xuan Wang and Shanpeng Wang","doi":"10.1039/D5CE00708A","DOIUrl":"https://doi.org/10.1039/D5CE00708A","url":null,"abstract":"<p >Mid-infrared (MIR) ultrafast lasers, generated through nonlinear frequency conversion using nonlinear optical (NLO) crystals, play a critical role in various fields, including ultrafast dynamics and biomedical applications. LiGaS<small>₂</small> (LGS) crystals are highly promising due to their broad band transparency, high thermal conductivity, high laser damage threshold and high chemical stability, which minimizes two-photon absorption under pump lasers. However, achieving high-quality LGS crystals <em>via</em> the Bridgman method is challenging due to lithium's corrosiveness and sulfur's high vapor pressure at growth temperatures. To obtain high-quality LGS crystals, numerical simulations were conducted to optimize the Bridgman growth process, including the optimal temperature field and growth parameters. Using the optimized Bridgman technique with spontaneous nucleation, high-quality LGS single crystals were successfully grown with dimensions of <em>Ø</em>12 mm × 30 mm. The crystal exhibits a UV absorption edge at 318 nm (optical bandgap 3.90 eV), an infrared cutoff at 12.8 μm, high transmittance (up to 80%) in the 0.4–8.6 μm wavelength range, and excellent crystallinity with a full width at half-maximum (FWHM) of 36′′ in the rocking curves. This work establishes a versatile strategy utilizing numerical simulation-guided optimization for the successful growth of high-quality ternary MIR chalcogenides <em>via</em> the Bridgman method.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 38","pages":" 6350-6359"},"PeriodicalIF":2.6,"publicationDate":"2025-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145183995","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":"Experimental and theoretical investigations of the optical and photoluminescence behaviour of a tetramorphic ternary molecular salt cocrystal – a quantum crystallography perspective†","authors":"Atiyyah Salajee, Anna Krawczuk, Rudolph Erasmus and Andreas Lemmerer","doi":"10.1039/D5CE00338E","DOIUrl":"https://doi.org/10.1039/D5CE00338E","url":null,"abstract":"<p >Four polymorphs of the ternary molecular salt cocrystal complex (3-hydroxypyridinium)·(9-anthracenecarboxylate)·(trinitrobenzene) were isolated. In all four polymorphs proton transfer occurred from the carboxylic acid to the nitrogen atom of the pyridine ring to form ternary molecular salts. Form <strong>I</strong> crystallizes as orange needles/rods, form <strong>II</strong> crystallizes as red blocks, and forms <strong>III</strong> and <strong>IV</strong> both crystallize as orangey-yellow needles. Differential scanning calorimetry indicates that form <strong>II</strong> is the thermodynamically most stable form, further supported by energy lattices calculated within periodic boundary conditions. Quantum theory of atoms in molecules (QTAIM) analysis revealed strong hydrogen bonds and charge-transfer interactions, with notable variations in the strength of these interactions across the polymorphs. Polymorph <strong>I</strong> showed the strongest charge-assisted O–H⋯O hydrogen bonds, while polymorph <strong>II</strong> displayed the most significant π⋯π interactions. Photoluminescence and UV-vis studies showed that the polymorphs exhibit differing band gaps, correlating with their observed colours and electronic structures. These results emphasize the role of polymorphism in modulating the physical and chemical properties of multi-component molecular crystals.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 36","pages":" 5971-5982"},"PeriodicalIF":2.6,"publicationDate":"2025-08-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ce/d5ce00338e?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145057489","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":"Structural response of diiodobutenyl-bis-thioquinolinium triiodide to high pressure and theoretical study of mechanical properties†","authors":"I. D. Yushina, Yu. V. Matveychuk, N. E. Bogdanov, S. V. Adichtchev, A. S. Krylov, A. I. Stash, E. V. Boldyreva and E. V. Bartashevich","doi":"10.1039/D5CE00638D","DOIUrl":"https://doi.org/10.1039/D5CE00638D","url":null,"abstract":"<p >The response of the diiodobutenyl-bis-thioquinolinium triiodide crystal structure to hydrostatic compression from 1 atm to 4 GPa and mechanical stress was studied using experimental techniques (Raman and Brillouin spectroscopy, single-crystal X-ray diffraction) and periodic DFT modeling. A phase transformation above 2.5(1) GPa manifested itself by abrupt changes in the unit cell parameters and non-merohedral twinning. The changes in the band positions in the low-wavenumber region of Raman spectra were attributed to a change in the bridging hydrogen position in the N⋯H⋯N fragment and to the changes in the anion. The DFT modeling of the crystal structure on compression revealed the changes in the structural fragments that can explain why a high-pressure phase transition takes place.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 38","pages":" 6283-6294"},"PeriodicalIF":2.6,"publicationDate":"2025-08-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145184025","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":"Adsorption behavior of ZIF composites with different loading methods of lacunary polyoxometalates towards cationic dyes","authors":"Xinyue Niu, Chunhui Zhang, Chunjing Zhang and Meiqiong Gao","doi":"10.1039/D5CE00743G","DOIUrl":"https://doi.org/10.1039/D5CE00743G","url":null,"abstract":"<p >In this study, two novel composite materials, SiW<small>₁₁</small>@ZIF-67 and ZIF-67@SiW<small>₁₁</small>, were synthesized <em>via in situ</em> encapsulation and post-loading methods, respectively. By leveraging the high negative charge characteristics of the vacancy polyoxometalate (SiW<small>₁₁</small>) in synergy with the stability of the ZIF-67 framework, the adsorption performance for the cationic dye neutral red (NR) was significantly enhanced. Experimental results demonstrated that under alkaline conditions (pH 8–11), the adsorption capacities of both materials for NR exceeded 35.5 mg g<small>⁻¹</small>. SiW<small>₁₁</small>@ZIF-67 exhibited excellent structural stability and regeneration performance because the polyoxometalate was embedded in the cavities of ZIF-67 (the adsorption efficiency remained &gt;90% after multiple methanol elutions). In contrast, ZIF-67@SiW<small>₁₁</small> showed significantly accelerated adsorption kinetics (reaching 90% saturation within 1 min) due to the surface-exposed SiW<small>₁₁</small>. The combination of electrostatic interactions and hydrogen bonds synergistically enhanced the selective adsorption of NR (40% higher than that of the anionic dye methyl orange). This study provides an innovative strategy for the design of vacancy polyoxometalate/MOF composite materials. It lays a theoretical and technical foundation for the development of efficient, renewable adsorbents suitable for the treatment of industrial alkaline dye wastewater and paves the way for their extended applications in complex dye systems.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 36","pages":" 6065-6073"},"PeriodicalIF":2.6,"publicationDate":"2025-08-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145057555","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":"Radical cation salts of dinaphtho[2,3-b:2′,3′-f]thieno[3,2-b]thiophene: characteristic crystal structures and properties","authors":"Barun Dhara, Kirill Bulgarevich and Kazuo Takimiya","doi":"10.1039/D5CE00680E","DOIUrl":"https://doi.org/10.1039/D5CE00680E","url":null,"abstract":"<p >A series of radical cation salts of dinaphtho[2,3-<em>b</em>:2′,3′-<em>f</em>]thieno[3,2-<em>b</em>]thiophene (DNTT), which has been known as a high-mobility p-type organic semiconductor, prepared by the electrocrystallization method, were characterized. In sharp contrast to the neutral DNTT in the solid state, which is characterized as a two-dimensional herringbone structure, all the radical cation salts of DNTT have a one-dimensional π-stacking structure of DNTT molecules, which are somewhat similar to those of the radical cation salts of [1]benzothieno[3,2-<em>b</em>][1]benzothiophene (BTBT), a lower homologue of DNTT. However, the electrical conductivities of the DNTT salts were far lower than those of the BTBT salts. The low conductivities of the DNTT salts were rationalized by the non-uniform columnar structure of the DNTT molecules with higher oxidation states than those of the BTBT salts. Such marked differences in conductivity could be boiled down to the π-extended molecular structure of DNTT, which can stabilize a higher oxidation state at the molecular level than that of BTBT and can create characteristic channel structures filled by counter anions and solvent molecules.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 38","pages":" 6333-6340"},"PeriodicalIF":2.6,"publicationDate":"2025-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145184021","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}