CrystEngComm最新文献

{"title":"What drives porosity in aluminosilicate zeolites?","authors":"Dries Vandenabeele, Anjul Rais, Christine Kirschhock, Eric Breynaert","doi":"10.1039/d5ce00034c","DOIUrl":"10.1039/d5ce00034c","url":null,"abstract":"<p><p>Discovery of their commercial potential gave rise to a massive implementation of zeolites in industrial (petro-)chemical processes. Their robustness and molecular scale porosity in combination with acidic and/or ion exchange properties makes zeolites nearly indispensable for most of these applications. This highlight explores the origins of zeolite porosity. As microporosity is an inherent feature of the formed topology, we emphasize the link with phase selection. For zeolites, phase selection is driven by competition between water and framework elements to coordinate with extra-framework species. This competition is important in the final product, where such coordinations provide thermodynamic stability, as well as in the crystallization medium where supermolecular structrures can play a templating role. Synthesis experiments using hydrated silicate ionic liquids show that limited water availability prompts the formation of less porous (or even dense) phases, while moderate hydration supports the development of more open frameworks. Understanding these interactions is key to deepening the insight into zeolite genesis and can guide strategies for tailoring material properties for industrial applications.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" ","pages":""},"PeriodicalIF":2.6,"publicationDate":"2025-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11934025/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143727193","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":"Mechanistic study on the crystal habit of 3,3′-diaminobenzidine in the presence of solvents and additives†","authors":"Jiawei Zhao, Na Wang, Lina Zhou, Ting Wang, Xin Huang, Ailian Wang, Longgui Zhang and Hongxun Hao","doi":"10.1039/D4CE01237B","DOIUrl":"https://doi.org/10.1039/D4CE01237B","url":null,"abstract":"<p >In this study, the solubility of 3,3′-diaminobenzidine in two mixed solvents (<em>N</em>,<em>N</em>-dimethylacetamide + water and dimethyl sulfoxide + water) was determined. The affecting mechanism of solvents and additives on the crystal behavior of 3,3′-diaminobenzidine was discussed. The interactions between 3,3′-diaminobenzidine and solvents or additives were analyzed from the aspects of crystal surface properties, diffusion coefficient, surface electrostatic potential distribution and radial distribution function. It was found that solvents and additives can significantly affect the crystal growth of 3,3′-diaminobenzidine in many ways. Hydrogen bonding and van der Waals forces play major roles in crystal packing. The interaction between solvent and crystal face can affect the growth of 3,3′-diaminobenzidine in different solvents by synergistic action. The presence of additives would affect the diffusion of molecules near the crystal surface and additive molecules are more easily adsorbed on (1 1 −1) and (1 0 0) faces. Meanwhile, the interaction between the (1 1 −1) face and additives is stronger and hence the area of the (1 1 −1) face is the largest in the final crystal habit. These findings could provide thermodynamic basis for the development of separation and purification technology for 3,3′-diaminobenzidine products, as well as theoretical guidance for regulating the crystal habit of 3,3′-diaminobenzidine crystals.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 14","pages":" 2204-2222"},"PeriodicalIF":2.6,"publicationDate":"2025-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143740573","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":"Yellow and red polymorphic co-crystals of phenyl-substituted pyrazinacene and naphthalene via π-hole⋯π interactions†","authors":"Kazushi Nakada, Gary J. Richards and Akiko Hori","doi":"10.1039/D5CE00114E","DOIUrl":"https://doi.org/10.1039/D5CE00114E","url":null,"abstract":"<p >The phenyl-substituted dicyanoazanaphthalene (<strong>1</strong>, C<small>₂₀</small>H<small>₁₀</small>N<small>₆</small>) is a yellow compound that forms both yellow and red crystals upon co-crystallization with naphthalene (<strong>2</strong>). These crystals represent a rare example of the polymorphism of <strong>1·2</strong>, forming two stable states, elucidating the role of donor–acceptor and π-hole⋯π interactions in the co-crystallization process. The yellow columnar crystal features an alternating arrangement of <strong>1</strong> and <strong>2</strong>, while the red plate crystal exhibits paired <strong>1</strong> and <strong>2</strong> units arranged in a herringbone motif. Although no significant differences in molecular structures were observed, the red crystal, at 160 K, exhibited a higher density (<em>D</em><small>_c</small> = 1.332 g cm<small>⁻³</small>) and planarity of the pyrazinacene framework compared to the yellow crystal (<em>D</em><small>_c</small> = 1.294 g cm<small>⁻³</small>), which correlates with its distinct optical and luminescent behaviors.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 14","pages":" 2064-2069"},"PeriodicalIF":2.6,"publicationDate":"2025-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143740538","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":"Effect of coordinated and lattice neutral co-ligands on the dielectric properties of cadmium and magnesium based coordination polymers†","authors":"Balendra, Mahboob Ali, Sanyukta and Sevi Murugavel","doi":"10.1039/D4CE01238K","DOIUrl":"https://doi.org/10.1039/D4CE01238K","url":null,"abstract":"<p >Two new coordination polymers, CPs [Cd<small>₂</small>(FBA)<small>₂</small>(DMA)<small>₂</small>]·THF (<strong>1</strong>) and [Mg<small>₃</small>(SBA)<small>₂</small>(EtOH)<small>₂</small>(H<small>₂</small>O)<small>₂</small>(μ<small>₃</small>-OH)<small>₂</small>]·DMA (<strong>2</strong>) {where, FBA = 4,4′ (hexafluoroisopropylidene)bisbenzoate, SBA = 4,4′-sulfonyldibenzoate, THF = tetrahydrofuran and DMA = <em>N</em>,<em>N</em>-dimethylacetamide}, were synthesized from cadmium and magnesium salts, 1,10-phenanthroline and two different V-shaped flexible ligands by solvothermal methods. The structures were determined by using single crystal X-ray diffraction analysis which revealed that solid <strong>1</strong> crystallizes in the monoclinic space group (<em>P</em>2/<em>n</em>) and adopts a 2D square channel structure with a unique dimeric {Cd<small>₂</small>O<small>₁₂</small>}<small>_<em>n</em></small> secondary building unit (SBU). Solid <strong>2</strong> also showed a 2D square channel structure and crystallizes in the monoclinic space group <em>C</em>2/<em>c</em> with an extended trimeric SBU of {Mg<small>₃</small>(μ<small>₃</small>-OH)O<small>₂₂</small>}<small>_<em>n</em></small>. The dielectric measurement study showed dielectric constants (<em>κ</em>) of ∼10.5 for <strong>1</strong> and ∼12.6 for <strong>2</strong> at room temperature. The values of the dielectric constants (<em>κ</em>) of solids <strong>1</strong> and <strong>2</strong> decreased significantly to values of ∼4.6 (solid <strong>1′</strong>) and ∼5.6 (solid <strong>2′</strong>) after removing the polar solvents, indicating that neutral co-ligand molecules present in the framework significantly affect the material dielectric behaviour. Furthermore, the investigation of impedance spectroscopy (<em>Z</em>′ and <em>Z</em>′′) revealed that the low and high dielectric constant values in the reported solids are attributed to the inherent properties of the bulk material. The reported work offers a suitable example for the construction of high and low-<em>κ</em> coordination polymers (CPs) as gate and interlayer dielectrics for electronic devices by altering the polar solvents present in the framework.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 14","pages":" 2136-2147"},"PeriodicalIF":2.6,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143740546","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":"Silver oxide-mediated synergistic enhancement of conductivity and adhesion in low-temperature cured silver pastes","authors":"Yi-Chen Guo, Xiao-Gang Liao, Qi Wu, Yu-Xuan Hao, Zi-Hao Wang, Wen-Yan Zhang and Yao-Yu Wang","doi":"10.1039/D4CE01120A","DOIUrl":"https://doi.org/10.1039/D4CE01120A","url":null,"abstract":"<p >Enhancing the conductivity of silver paste is crucial for achieving high photoelectric conversion efficiency of heterojunction solar cells. In this work, 1-tetradecanol-coated Ag<small>₂</small>O was used as a silver precursor, replacing nano-silver powder in the conventional silver paste. Low-temperature sintering (200 °C) was utilized to establish a conductive pathway between flaky and spherical silver powder, resulting in a low-cost, low-temperature cured silver paste. The effect of 1-tetradecanol content on Ag<small>₂</small>O was investigated, focusing on the electrical conductivity, silver paste rheological properties and adhesion properties of low-temperature cured silver paste film layers. The results showed that the volume resistivity of the paste containing 1-tetradecanol (10 wt%)-coated Ag<small>₂</small>O after sintering at 200 °C for 30 min was 7.44 × 10<small>⁻⁵</small> Ω cm, which was 35% lower than that of pure silver powder paste, indicating a significant enhancement in electrical conductivity. Furthermore, rheological performance tests demonstrated that the incorporation of Ag<small>₂</small>O was an effective route for enhancing the thixotropy, recovery, and stability of the paste. Meanwhile, an adhesion experiment demonstrated that silver pastes with introduced Ag<small>₂</small>O (≥5 wt%) exhibited a robust bonding to the ITO substrate under low-temperature curing, with an ASTM grade of 5B.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 14","pages":" 2166-2174"},"PeriodicalIF":2.6,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143740569","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":"Second harmonic generation and crystal structure of a self-assembled Boc-p-nitro-l-phenylalanyl-p-nitro-l-phenylalanine dipeptide†","authors":"Rosa M. F. Baptista, Alejandro P. Ayala, Etelvina de Matos Gomes, M. Cidália R. Castro, Ana V. Machado and Michael S. Belsley","doi":"10.1039/D5CE00134J","DOIUrl":"https://doi.org/10.1039/D5CE00134J","url":null,"abstract":"<p >(Boc = <em>tert</em>-butoxycarbonyl)-<em>p</em>-nitro-<small>L</small>-phenylalanyl-<em>p</em>-nitro-<small>L</small>-phenylalanine, a dipeptide characterised by acentric symmetry, self-assembles into microtapes. This study explores its thermal, structural, and nonlinear optical properties. Thermogravimetric Analysis reveals an onset degradation temperature of 190 °C, with primary and secondary peaks at 202 °C and 220 °C, respectively. The crystal structure of the dipeptide was determined through single crystal X-ray diffraction at 100 K, confirming its crystallisation in a monoclinic crystal lattice, space group <em>P</em>2 with two molecules per unit cell. Additionally, optical second harmonic generation polarimetry indicates a nonlinear optical response, with an effective coefficient (<em>d</em><small>_eff</small>) estimated to be at least 0.67 pm V<small>⁻¹</small>. This value is only four times lower than that of a state-of-the-art phase-matched oriented β-barium borate nonlinear crystal. The crystal is unusually robust against optical damage for an organic crystal, underlining the potential of this dipeptide in nonlinear optical applications.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 14","pages":" 2195-2203"},"PeriodicalIF":2.6,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143740572","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":"Reactive crystallization of Li2CO3 in LiOH/KOH solutions: solubility, nucleation and carbonization†","authors":"Zhuofan Chen, Yuhao Chen, Youfa Jiang, Chenglin Liu and Jianguo Yu","doi":"10.1039/D4CE01106F","DOIUrl":"https://doi.org/10.1039/D4CE01106F","url":null,"abstract":"<p >Lithium carbonate (Li<small>₂</small>CO<small>₃</small>) is essential for lithium-ion battery production, which is pivotal for the advancement of new energy technologies. While extensive research has been conducted on Li<small>₂</small>CO<small>₃</small> crystallization in neutral solutions, there is a notable gap in understanding its behavior in alkaline environments, which could enhance the efficiency of its production. This study addresses this gap by investigating the reactive crystallization of Li<small>₂</small>CO<small>₃</small> from LiOH/KOH mixed solutions. The solubility, nucleation, and carbonation processes of Li<small>₂</small>CO<small>₃</small> in KOH solution were determined. Increasing temperature and decreasing KOH concentration would reduce the solubility of Li<small>₂</small>CO<small>₃</small>. Furthermore, higher temperatures were found to accelerate Li<small>₂</small>CO<small>₃</small> precipitation and improve lithium recovery rates, achieving an 85.68% recovery with high crystallinity and purity of 98.4% at 363.15 K. The optimized temperature and KOH concentration can significantly enhance Li<small>₂</small>CO<small>₃</small> crystallization in alkaline solutions. This advancement addresses a critical knowledge gap and provides a valuable reference for the recycling of lithium resources as well as the development of novel preparation processes.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 14","pages":" 2115-2123"},"PeriodicalIF":2.6,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143740544","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":"Exploring quaternary vanadates containing alkali metals, alkaline earth metals, and [VO4] in the quest for nonlinear optical materials†","authors":"Xiaoming Wang, Qiuyuan Feng, Ketian Hou, Wei Wei, Juanjuan Lu, Lai Wei and Feng Zhang","doi":"10.1039/D4CE01058B","DOIUrl":"https://doi.org/10.1039/D4CE01058B","url":null,"abstract":"<p >VO<small>₄</small> units are highly susceptible to distortion induced by crystal fields, and thus, they are favorable for generating second-order nonlinear optical properties in the visible-light frequency range. Among the quaternary compounds containing VO<small>₄</small> units, vanadates with cations of alkali metals and/or alkaline earth metals exhibit a higher proportion of non-centrosymmetric structures, making them promising candidates for exploring nonlinear optical materials. However, to date, the optical properties of compounds within this category have rarely been characterized. In this work, we successfully synthesized two non-centrosymmetric compounds, NaMg<small>₄</small>(VO<small>₄</small>)<small>₃</small> and LiMg<small>₄</small>(VO<small>₄</small>)<small>₃</small>. Experimental results showed that NaMg<small>₄</small>(VO<small>₄</small>)<small>₃</small>, which has a bandgap of 3.14 eV, showed a second-harmonic generation response of 1.1 × KDP and 0.4 × AGS at its maximum particle size. LiMg<small>₄</small>(VO<small>₄</small>)<small>₃</small>, with a bandgap of 3.10 eV, showed a second-harmonic generation response of 0.7 × KDP and 0.1 × AGS at its maximum particle size. NaMg<small>₄</small>(VO<small>₄</small>)<small>₃</small> could achieve phase matching at the fundamental frequency of 2090 nm but not at 1064 nm. LiMg<small>₄</small>(VO<small>₄</small>)<small>₃</small> was unable to achieve phase matching at both the fundamental frequencies of 1064 nm and 2090 nm. In summary, we conducted a systematic investigation of quaternary compounds containing alkali and alkaline earth metal cations and VO<small>₄</small> anions and performed a comprehensive characterization of the nonlinear optical properties of NaMg<small>₄</small>(VO<small>₄</small>)<small>₃</small> and LiMg<small>₄</small>(VO<small>₄</small>)<small>₃</small>. The findings give insights into designing new vanadate-based compounds for the application of nonlinear optical materials in the future.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 14","pages":" 2101-2107"},"PeriodicalIF":2.6,"publicationDate":"2025-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143740542","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":"Inclusion and intercalation compounds of arsenic(iii) oxide polymorphs†","authors":"Piotr A. Guńka","doi":"10.1039/D5CE00135H","DOIUrl":"https://doi.org/10.1039/D5CE00135H","url":null,"abstract":"<p >Arsenic(<small>III</small>) oxycompounds exhibit rich structural chemistry due to the presence of stereoactive lone electron pairs on arsenic and secondary As⋯O bonds that stabilize variable conformations of chains and rings in the case of oxyanions and layers or molecules in the case of oxide. These two features are also responsible for the fact that arsenic(<small>III</small>) oxide forms inclusion and intercalation compounds. In this Highlight article, the discovery and characterization of molecular arsenic(<small>III</small>) oxide inclusion compounds with hydrogen and helium are presented. Also, structural studies of As<small>₂</small>O<small>₃</small> intercalation compounds with alkali metal halides and pseudohalides are thoroughly described. Finally, future research avenues in the field are presented, which have become more appealing due to the recent literature reports of extraordinary optical properties of arsenic(<small>III</small>) oxide intercalates.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 13","pages":" 1862-1872"},"PeriodicalIF":2.6,"publicationDate":"2025-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ce/d5ce00135h?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143688238","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":"Synergistic advantages of In-MOF/Bi2MoO6 composites in photocatalytic CO2 reduction: enhanced light absorption, charge separation and reactivity†","authors":"Xiao Zhang, Xiong He, Meng-Yao Ye, Bei-Bei Yuan, Song-Fang Zhao and Kui Li","doi":"10.1039/D4CE01285B","DOIUrl":"https://doi.org/10.1039/D4CE01285B","url":null,"abstract":"<p >The development of highly efficient photocatalysts for the reduction of CO<small>₂</small> holds paramount importance in addressing the pressing global energy and environmental challenges. In this meticulously conducted study, we successfully fabricated a novel composite consisting of In-MOF and Bi<small>₂</small>MoO<small>₆</small>, and comprehensively investigated its photocatalytic performance in the context of CO<small>₂</small> reduction. The formation of a heterojunction between the In-MOF and Bi<small>₂</small>MoO<small>₆</small> facilitated efficient charge separation and transfer processes. The internal electric field present at the interface of the heterojunction drove the photogenerated electrons and holes to migrate in opposite directions, effectively mitigating their recombination rate. Consequently, a greater abundance of reactive species was available to participate in the CO<small>₂</small> reduction reaction. The combined effects of enhanced light absorption and efficient charge separation culminated in a higher yield of CO and CH<small>₄</small> compared to the individual components. This study provides some references and insights into the design and manufacture of high-performance photocatalysts.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 12","pages":" 1694-1700"},"PeriodicalIF":2.6,"publicationDate":"2025-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143632272","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}