CrystEngComm最新文献

{"title":"A new silver–thiolate nanocluster synthesized utilizing pure-inorganic polyoxoniobate as a starting template and its variable-temperature fluorescence properties†","authors":"Li Zeng, Ya-Ting Lin, Li-Hao Hong, Yan-Qiong Sun, Jianping Xie, Shou-Tian Zheng and Xin-Xiong Li","doi":"10.1039/D5CE00195A","DOIUrl":"https://doi.org/10.1039/D5CE00195A","url":null,"abstract":"<p >In the past, the synthesis of polyoxometalate (POM)-templated silver nanoclusters typically relied on the use of organic salts of POMs as starting templates, thereby limiting the solvent selectivity in the synthesis. The utilization of pure-inorganic POMs as starting templates in developing novel POM-templated silver nanoclusters has been neglected. Herein, we have used pure-inorganic polyoxoniobates as a starting template to synthesize a new silver nanocluster H<small>₄</small>[Nb<small>₆</small>O<small>₁₉</small>@Ag<small>₄₀</small>(<small>^<em>i</em></small>PrS)<small>₂₈</small>S<small>₄</small>] (<strong>Ag<small>₄₀</small></strong>) (<small>^<em>i</em></small>PrS = isopropylthiolate). Single-crystal X-ray diffraction analysis showed that the silver nanocluster exhibits a remarkable core–shell structure featuring a Lindqvist-type [Nb<small>₆</small>O<small>₁₉</small>]<small>⁸⁻</small> polyanion as a template, surrounded by 40-nucleated silver ions as the metal shell and capped by <small>^<em>i</em></small>PrS<small>⁻</small> ligands. Interestingly, the silver nanocluster exhibits significant fluorescence properties at low temperatures, demonstrating temperature-dependent fluorescence, making it a potential candidate for temperature sensing. This work provides a new strategy for new POM-templated silver nanoclusters by using pure-inorganic POMs as starting templates. It also offers new insights into the anionic template method for synthesizing silver nanoclusters.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 18","pages":" 2883-2887"},"PeriodicalIF":2.6,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143908492","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":"Synthesis of dual-state emissive twisted donor–acceptor fluorophores: tunable fluorescence and self-reversible mechanofluorochromism†","authors":"Sasikala Ravi, R. Rameshbabu Priyadharsan, Subramanian Karthikeyan, Mehboobali Pannipara, Abdullah G. Al-Sehemi, Dohyun Moon and Savarimuthu Philip Anthony","doi":"10.1039/D4CE01317D","DOIUrl":"https://doi.org/10.1039/D4CE01317D","url":null,"abstract":"<p >Exploring new organic solid-state fluorescent molecules with tunable and switchable fluorescence is of fundamental importance for understanding the structure–property relationship and developing efficient materials for device applications. Herein, we have designed and synthesized blue-emitting cyanophenyl ether attached triphenylamine (TPA)-based donor–acceptor derivatives (CPDB-MN, CPDB-ECA, CPDB-CA, CPDB-CAA and CPDB-MBA) and investigated their solid-state fluorescence and stimuli-responsive fluorescence switching. All five fluorophores exhibited tunable dual-state (solution and solid-state) emission, depending on the solvent polarity and acceptor functionality. The CPDB derivatives showed dual fluorescence at shorter and longer wavelengths in solution, which might be attributed to the integration of blue-emitting cyanophenyl with the TPA donor–acceptor unit. In the solid-state, these derivatives showed aggregation-induced emission (AIE), predominantly from the TPA donor–acceptor system. The CPDB molecules exhibited tunable solid-state fluorescence between 532 and 615 nm (quantum yield (<em>Φ</em><small>_f</small>) = 1.02% to 14.14%). Solid-state structural analysis revealed that cyanophenyl and diphenylamine adopted different conformations depending on the acceptor. Weak intermolecular interactions in the crystal lattice created a network structure and increased structural rigidity in the solid-state. Computational studies further supported the conformational changes, showing that acceptors influenced the optical bandgap and fluorescence tuning. Notably, CPDB-CA displayed mechanical stimuli-responsive reversible/self-reversible fluorescence switching due to a reversible phase transition. Powder X-ray diffraction (PXRD) was performed to gain insights into fluorescence switching and phase transitions. Thus, the present work studied the effect of the acceptor unit on the molecular conformation and solid-state fluorescence.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 17","pages":" 2759-2766"},"PeriodicalIF":2.6,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143861017","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 study of the influence regularity of caprolactam on the crystallisation of ammonium sulphate in aqueous solution","authors":"Meiqi Zhang, Xiang Sun, Xiaoyu Ma and Xunqiu Wang","doi":"10.1039/D4CE01288G","DOIUrl":"https://doi.org/10.1039/D4CE01288G","url":null,"abstract":"<p >The crystal size of ammonium sulphate, a by-product of caprolactam production, is generally less than 1 mm. In order to increase the crystal size, a detailed study of the crystallisation process is required. In this paper, we investigated the effects of crystalline species, rotational speed, cooling rate and caprolactam addition on the crystallisation process of ammonium sulphate. The kinetic equation of ammonium sulphate nucleation and the kinetic equation of ammonium sulphate growth were obtained by fitting the optimised Δ<em>L</em> law model. The results showed that <em>B</em> = 1.0334 × 10<small>⁻¹⁴</small><em>τ</em><small>^0.3071</small>, <em>G</em> = 2.1997<em>τ</em><small>^−0.4792</small> with a rotational speed of 450 r min<small>⁻¹</small>, a cooling rate of 0.25 K min<small>⁻¹</small>, the absence of crystal seed and without the addition of caprolactam. When caprolactam was added at 1.04%: <em>B</em> = 1.5946 × 10<small>⁻²¹</small><em>τ</em><small>^2.1423</small>, <em>G</em> = 5.097<em>τ</em><small>^−0.4792</small> while other conditions remained the same. When ammonium sulphate solution contains caprolactam, the nucleation rate of ammonium sulphate increases while the growth rate decreases. The nucleation rate of ammonium sulphate increases gradually with the increase of the mass fraction of caprolactam and the growth rate decreases slowly with the increase of the mass fraction of caprolactam.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 18","pages":" 2872-2882"},"PeriodicalIF":2.6,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143908491","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":"Structures and band gaps of lead-free dabconium-containing hybrid alkali-metal halide perovskites†","authors":"Hendrik J. van der Poll, Rudolph Erasmus and Melanie Rademeyer","doi":"10.1039/D4CE00907J","DOIUrl":"https://doi.org/10.1039/D4CE00907J","url":null,"abstract":"<p >Ten hybrid metal halide perovskites containing divalent dabconium cations and alkali-metal ions have been structurally characterised and their band gaps determined, with six new crystal structures reported. Five compounds of the formula (C<small>₆</small>H<small>₁₄</small>N<small>₂</small>)[BX<small>₃</small>], where B = Na<small>⁺</small> and X = Cl<small>⁻</small> or Br<small>⁻</small>, B = K<small>⁺</small> and X = Cl<small>⁻</small> or Br<small>⁻</small> and B = Cs<small>⁺</small> and X = I<small>⁻</small>, were found to exhibit one-dimensional (1D) hexagonal perovskite structures containing face-sharing metal halide octahedra that form 1D inorganic polymers. Five compounds of the formula (C<small>₆</small>H<small>₁₄</small>N<small>₂</small>)[BX<small>₃</small>], where B = K<small>⁺</small> and X = Br<small>⁻</small> or I<small>⁻</small>, and B = Cs<small>⁺</small> and X = Cl<small>⁻</small>, Br<small>⁻</small> or a mixture of Cl<small>⁻</small> and I<small>⁻</small>, display three-dimensional (3D) parent perovskite structures containing corner sharing metal halide octahedra that form a 3D framework. A correlation was found between the formation of a 1D or 3D perovskite structure and the sum of ionic radii of the metal and halide ions. The band gaps of the compounds fall in the range 3.42 eV to 5.33 eV. It was found that a 3D perovskite has a smaller band gap than a 1D perovskite, while the halide ion also affects the band gap.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 16","pages":" 2545-2558"},"PeriodicalIF":2.6,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ce/d4ce00907j?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143835496","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":"A flexible molecular organic crystal with π–π bonding for the highly selective recognition of hydrogen isotopes†","authors":"Min Lei, Lisha Jiang, Chunhui Wang, Jianxin Song, Wei Liu and Jie Qiu","doi":"10.1039/D5CE00221D","DOIUrl":"https://doi.org/10.1039/D5CE00221D","url":null,"abstract":"<p >Deuterium oxide (D<small>₂</small>O) is widely used in diverse fields, notably as a moderator in heavy water reactors, for electrolytic extraction of deuterium gas, and in nuclear magnetic resonance (NMR) research. However, it exhibits a high susceptibility to H<small>₂</small>O contamination. Herein, a fluorescent hydrogen-bonded molecular organic crystal (ASP-101) with robust π–π interactions was synthesized by using 5,5′-(9,10-anthracene diphenyl dicarboxylic acid) (H<small>₄</small>ADIP) and dimethyl sulfoxide (DMSO). Distinct fluorescence quenching phenomena were observed when ASP-101 was soaked in H<small>₂</small>O and D<small>₂</small>O. Based on these phenomena, subsequent studies demonstrated that ASP-101 is capable of detecting trace amounts of H<small>₂</small>O in D<small>₂</small>O, with a <em>K</em><small>_SV</small> value of 6 × 10<small>⁻²</small> M<small>⁻¹</small> and a detection limit of 6.5 × 10<small>⁻³</small> M (0.117 ppm). Batch experiments proved that the DMSO molecules within ASP-101 undergo exchange with H<small>₂</small>O and D<small>₂</small>O after soaking in aqueous solution. Previous research had found that deuteration can affect the emission properties of organic molecules. Thus, ASP-101's ability to detect H<small>₂</small>O in D<small>₂</small>O may be attributed to the fluorescent difference arising from the incorporation of H<small>₂</small>O and D<small>₂</small>O into its structure <em>via</em> solvent exchange. This study presents an authentic scenario for advancing isotopic identification based on alterations in fluorescence induced by solvent exchange.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 16","pages":" 2591-2599"},"PeriodicalIF":2.6,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143835499","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":"Fabrication of an efficient bifunctional acid catalyst based on MIL-88B(Fe) for solvent-free ring-opening of epoxides with alcohols†","authors":"Mahdiyeh-Sadat Hosseini, Alireza Abbasi, Peyman Ghorbani and Majid Masteri-Farahani","doi":"10.1039/D4CE01072H","DOIUrl":"https://doi.org/10.1039/D4CE01072H","url":null,"abstract":"<p >A new bifunctional heterogeneous acid catalyst with both Lewis and Brønsted acid sites was successfully synthesized <em>via</em> the post-synthetic modification (PSM) method. To this end, a stable metal–organic framework (MOF), namely MIL-88B(Fe), with several coordination unsaturated sites (CUSs) as Lewis acids was modified with sulfamic acid to increase the acidity of the MOF. Both X-ray diffraction (XRD) and N<small>₂</small> sorption techniques confirmed the introduction of sulfamic acids into the MOF structure through the displacement of the (101) crystal plane to lower angles and increase in the surface area (BET method) and pore volume, respectively, owing to the swelling effect of this MOF. Furthermore, the existence of sulfamic acids in the backbone of the MIL-88B(Fe)/SA catalyst was detected using energy dispersive X-ray (EDX) and FT-IR analyses. The solvent-free ring-opening of styrene oxide with methanol was initially conducted to evaluate the catalytic performance of the catalyst. Compared to MIL-88B(Fe) with Lewis acidity, bifunctional MIL-88B(Fe)/SA demonstrated the highest styrene oxide conversion (95%) owing to the synergy between Lewis and Brønsted acid sites. Besides, some epoxides and alcohols were utilized in this catalytic reaction, and its reusability and stability were found excellent in consecutive catalytic runs.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 17","pages":" 2729-2738"},"PeriodicalIF":2.6,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143861014","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":"Bright electrospun white Y2Zr2O7:Tm3+/Dy3+ nanotubes with excellent thermal quenching resistance and ultralow color shift†","authors":"Shanshan Cong, Hongquan Yu, Zhichao Ren, Jiashi Sun, Xiangping Li, Sai Xu and Baojiu Chen","doi":"10.1039/D5CE00133A","DOIUrl":"https://doi.org/10.1039/D5CE00133A","url":null,"abstract":"<p >White LEDs are environmentally friendly light sources that have received extensive attention. The combination of an ultraviolet chip and three-color phosphors is the main method used to obtain white LED devices. The primary issues include the decrease in the luminescence intensity and lifetime, the reduction in the output power of the LED device, and the color shift of the phosphor in high-temperature environments caused by high operating currents and prolonged working times. In this work, bright single-phase full-spectrum white Tm<small>³⁺</small> and Dy<small>³⁺</small> Y<small>₂</small>Zr<small>₂</small>O<small>₇</small> (YZO) nanotubes with high thermal stability and ultralow color drift were prepared by an electrospinning technique at 1300 °C. The color coordinates (0.3308, 0.332) of YZO:2%Tm<small>³⁺</small>/2%Dy<small>³⁺</small> nanotubes are very close to those of standard white light (0.33, 0.33). The luminescence properties of YZO:Tm<small>³⁺</small>/Dy<small>³⁺</small> nanotubes were investigated and compared with those of YZO:Tm<small>³⁺</small>/Dy<small>³⁺</small> powders prepared <em>via</em> a solid-state reaction at 1300 °C. At high temperatures, YZO:Tm<small>³⁺</small>/Dy<small>³⁺</small> nanotubes exhibit better thermal quenching resistance than YZO:Tm<small>³⁺</small>/Dy<small>³⁺</small> powders do because of their unique tubular structure. YZO:2%Tm/1%Dy nanotubes retains 91.23% of their initial emission intensity at 453 K compared to that at 303 K, whereas the emission intensity of YZO:2%Tm/1%Dy powders remains at 90.42% at 453 K compared to that at room temperature. YZO:2%Tm/1%Dy nanotubes have an ultralow color drift of 0.16% at 453 K, whereas that of YZO:2%Tm/1%Dy powders reaches 0.9% at the same temperature.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 17","pages":" 2748-2758"},"PeriodicalIF":2.6,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143861016","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":"Polymorphs and stoichiometric variants of crown ether-based molecular complexes: exploring the landscape of conformational flexibility and supramolecular interactions†","authors":"Cinu Winson, Saravanan Kandasamy, Indira S. Divya, Krzysztof Wozniak and Sunil Varughese","doi":"10.1039/D5CE00025D","DOIUrl":"https://doi.org/10.1039/D5CE00025D","url":null,"abstract":"<p >Leveraging supramolecular interactions, we explored the structural diversity of molecular complexes formed from crown ethers and dithiooxamide (DTX) or 3,5-dinitroaniline (DNA). In our attempts to obtain ternary systems, co-crystallization was done in the presence or absence of halogenated compounds to utilize the orthogonality of the supramolecular interactions—hydrogen and halogen bonds. Nevertheless, binary complexes predominated but in diverse crystal forms. Though not present in the crystal lattice, the halogenated compounds, as scaffolds, are critical in attaining the conformational diversity in the crown ethers. The structural diversity in the multi-component systems highlights the versatility of interactions and the conformational flexibility of crown ethers. The adaptable nature of crown ethers facilitated interactions with coformers, resulting in complexes of varied stoichiometries. Experimental and computational analyses reveal distinct conformational motifs favoured by these molecules, influencing interaction profiles and crystal forms. This study underscores the importance of understanding molecular flexibility and diverse interactions for material synthesis and molecular design.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 17","pages":" 2698-2710"},"PeriodicalIF":2.6,"publicationDate":"2025-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143861054","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":"What drives porosity in aluminosilicate zeolites?","authors":"Dries Vandenabeele, Anjul Rais, Christine Kirschhock and Eric Breynaert","doi":"10.1039/D5CE00034C","DOIUrl":"10.1039/D5CE00034C","url":null,"abstract":"<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":" 16","pages":" 2452-2461"},"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":"The effect of viologen counterions on the topologies of La(iii)–tetraoxolene metal–organic frameworks†","authors":"Yuying Feng, Carol Hua and Martin P. van Koeverden","doi":"10.1039/D5CE00026B","DOIUrl":"https://doi.org/10.1039/D5CE00026B","url":null,"abstract":"<p >Lanthanoid containing coordination polymers and metal–organic frameworks (MOFs) have attracted significant attention due to their potential application in photoluminescence, high-density information storage, and chemical sensing. Controlling the connectivity of the frameworks is a crucial goal, as both the physical and chemical properties of these compounds are closely related to their network topologies. Two viologen cations have been investigated for their structure directing effects in the synthesis of La(<small>III</small>)–tetraoxolene frameworks containing F, Cl and Br substituents. The framework topologies obtained demonstrate the potential for viologen cations to influence the structure of the La–tetraoxolene MOFs through non-covalent interactions.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 16","pages":" 2559-2569"},"PeriodicalIF":2.6,"publicationDate":"2025-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143835497","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}