CrystEngComm最新文献

{"title":"A cobalt(ii)-terpyridine complex showing field-induced slow magnetic relaxation behavior via reverse spin-crossover†","authors":"Long Huang, Kun-Hua Zhang, Ao-Na Sun, Bingshan Zhao, Le Shi, Jiong Yang and Dong Shao","doi":"10.1039/D5CE00223K","DOIUrl":"https://doi.org/10.1039/D5CE00223K","url":null,"abstract":"<p >Multistable molecular magnetic materials that exhibit different magnetic bistability are highly attractive, however, materials showing multistabilities are relatively rare. Herein, we present a rare example of the coexistence of thermally-induced spin-crossover (SCO) and field-supported single-ion magnet (SIM) observed in a bromine-functionalized cobalt(<small>II</small>) complex [Co(Brphtpy)<small>₂</small>](PF<small>₆</small>)<small>₂</small> (Brphtpy = 4′-(4-bromophenyl)-2,2′:6′,2′′-terpyridine, <strong>1</strong>). The temperature-dependent magnetic susceptibility and differential scanning calorimetry experiment shows a gradual SCO behavior in the temperature range of 400–125 K with the <em>T</em><small>_1/2</small> = 325 K. Interestingly, reverse SCO behavior was observed below 125 K, which induces to a mixed high spin and low spin Co<small>²⁺</small> ions in complex <strong>1</strong>. At lower temperature, frequency- and temperature-dependent slow magnetic relaxation behaviors processed <em>via</em> Raman and direct relaxation were evidenced under an applied DC field of 1000 Oe with the estimated effective energy barrier being 26.2 K, possibly originating from the small fraction of high spin Co(<small>II</small>) ions or low spin Co(<small>II</small>) ions. This work provides not only a new bifunctional SCO–SIM complex but also a promising way for designing multi-stable molecular magnetic materials through reverse spin-crossover behavior.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 21","pages":" 3545-3551"},"PeriodicalIF":2.6,"publicationDate":"2025-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144140042","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":"The behaviour of two diamino-derived host compounds in cyclohexanone and isomeric methylcyclohexanones†","authors":"Danica B. Trollip, Benita Barton, Mino R. Caira and Eric C. Hosten","doi":"10.1039/D5CE00298B","DOIUrl":"https://doi.org/10.1039/D5CE00298B","url":null,"abstract":"<p >The present investigation centred around the host ability of two novel compounds, <em>N</em>,<em>N</em>′-bis(5-phenyl-5-dibenzo[<em>a</em>,<em>d</em>]cycloheptenyl)propane-1,3-diamine (<strong>DB3</strong>) and <em>N</em>,<em>N</em>′-bis(9-phenyl-9-thioxanthenyl)butane-1,4-diamine (<strong>S4</strong>), for guest solvents cyclohexanone and its methylcyclohexanone isomers (Cyc, 2MeCyc, 3MeCyc and 4MeCyc). While <strong>DB3</strong> formed complexes with each of these organic solvents, <strong>S4</strong> only included 4MeCyc. All complexes were characterized by 1 : 1 host : guest ratios. With the view to assessing whether these host compounds have the potential to separate mixtures of the cyclohexanones, each one was crystallized from various guest mixtures. It was determined that such separations would not be feasible through supramolecular chemistry strategies with these two host species owing to low calculated selectivity coefficients (<em>K</em>). This was despite the observed selectivity of <strong>DB3</strong> for 4MeCYC and Cyc in the mixed guest experiments. However, a thorough scrutiny of the five novel complexes was subsequently undertaken, and the crystal structures, through SCXRD analysis, demonstrated that Cyc, a preferred guest solvent, when included by <strong>DB3</strong>, occupied highly constricted channels, while these were comparatively wider and more open in the complexes with the MeCycs. Furthermore, preferred Cyc was the only guest molecule that engaged in a classical hydrogen bond with <strong>DB3</strong>, and Hirshfeld surface analyses showed this guest (which only has 10 hydrogen atoms) to be involved in the greater quantity of (guest)H⋯H(host) interactions (the MeCyc molecules have 12 hydrogen atoms and experienced less of this type of interaction). All of these observations provide an explanation for the affinity of <strong>DB3</strong> for Cyc (but not for 4MeCyc). These SCXRD analyses further demonstrated that the geometry of the diamino linker in the <strong>DB3</strong> complexes was more folded in nature while, in <strong>S4</strong>·4MeCyc, this was in an extended zig-zag orientation. Finally, thermal analyses on each of the complexes, unsurprisingly, demonstrated the Cyc-containing complex with <strong>DB3</strong> to be the most stable one.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 20","pages":" 3279-3294"},"PeriodicalIF":2.6,"publicationDate":"2025-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ce/d5ce00298b?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144090893","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":"Low-dimensional strategy of ultra-fast high-efficiency scintillators for X-ray imaging under indoor light interference†","authors":"Haitao Tang, Shaowei Feng, Qiping Du, Yichen Xu, Bin Yu, Zhenglin Jia, Yong Liu, Hailin Liu, Kunfeng Chen, Dongfeng Xue and Qianqian Lin","doi":"10.1039/D5CE00312A","DOIUrl":"https://doi.org/10.1039/D5CE00312A","url":null,"abstract":"<p >Metal halide perovskites are emerging as promising X-ray sensitive materials. However, their practical application as scintillators is hindered by low light yield and long radiative decay times. Here, we report lead-free Bmpip<small>₂</small>SnBr<small>₄</small>:12% Cu<small>⁺</small> hybrid halide single crystals. Thanks to the sensitization effect of Cu<small>⁺</small> ions with strong electron–phonon coupling, the photoluminescence quantum yield was increased from 67.74% to 86.01%. In addition, the interphase arrangement of organic and inorganic monomers in the 0-dimensional quantum well structure makes it difficult to transfer charge over a long distance, in which the large exciton binding energy leads to its attenuation of only 1.47 ns. The Bmpip<small>₂</small>SnBr<small>₄</small>:12% Cu<small>⁺</small> single crystals can be excited by X-rays, yielding a scintillation light output of 57 977 photons per MeV and a low detection limit of 32.59 nGyair s<small>⁻¹</small>. Furthermore, they demonstrate a spatial resolution of 22.8 lp mm<small>⁻¹</small>, which demonstrates their practical application potential in X-ray imaging under indoor optical crosstalk, characterized by high light yield, short decay time, low toxicity, and cost-effectiveness.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 19","pages":" 3143-3151"},"PeriodicalIF":2.6,"publicationDate":"2025-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143944085","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":"Hierarchical iodine(i) complexes of nicotinamide†","authors":"Sharath Mohan, Arto Valkonen, Kari Rissanen and Jas S. Ward","doi":"10.1039/D5CE00339C","DOIUrl":"https://doi.org/10.1039/D5CE00339C","url":null,"abstract":"<p >The incorporation of the 3-substituted pyridine derivative nicotinamide (<strong>1</strong>) into an iodine(<small>I</small>) complex gave the hierarchical iodine(<small>I</small>) complex, [I(nicotinamide)<small>₂</small>]PF<small>₆</small> (<strong>3</strong>), synthesised through cation exchange with I<small>₂</small> of the respective silver(<small>I</small>) complex, [Ag(nicotinamide)<small>₂</small>]PF<small>₆</small> (<strong>2</strong>). Complex <strong>3</strong> was characterised in both solution (<small>¹</small>H, <small>¹</small>H–<small>¹⁵</small>N HMBC), and extensively in the solid state by single-crystal X-ray diffraction (SCXRD) due to the various polymorphs and solvates observed. As only the second example of a hierarchical halogen(<small>I</small>) complex, analysis of the different hydrogen-bonding networks present in the solid-state variants of <strong>3</strong> allowed the relationship between the halogen and hydrogen bonding to be explored in more depth. The presence of the hydrogen bonds in the non-solvated solid-state structure of <strong>3</strong> (<strong>3_NS</strong>) was found to impart increased resilience to H<small>₂</small>O and acetic acid, all without diminishing its reactivity as an iodination reagent in comparison to Barluenga's reagent ([I(pyridine)<small>₂</small>]BF<small>₄</small>), as demonstrated <em>via</em> solution and mechanochemical reactivity studies with antipyrine.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 20","pages":" 3295-3301"},"PeriodicalIF":2.6,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ce/d5ce00339c?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144090894","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":"Correction: Two zinc(ii)-based coordination polymers as luminescent sensors for detecting salicylaldehyde with high sensitivity and selectivity","authors":"Ruo-Tong Gang, Wen-Jing Zhang, Hai-Jun Yu, Zhen-Hui Li, Yi-Long Li, Xue-Ru Wu, Ming-Guang Chen, Shu-Man Gao and Feng Shao","doi":"10.1039/D5CE90061A","DOIUrl":"https://doi.org/10.1039/D5CE90061A","url":null,"abstract":"<p >Correction for ‘Two zinc(<small>II</small>)-based coordination polymers as luminescent sensors for detecting salicylaldehyde with high sensitivity and selectivity’ by Ruo-Tong Gang <em>et al.</em>, <em>CrystEngComm</em>, 2025, https://doi.org/10.1039/d4ce01236d.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 18","pages":" 2952-2952"},"PeriodicalIF":2.6,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ce/d5ce90061a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143908500","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":"Photosalient [2 + 2] photodimerization in metal chloride-templated organic crystals†","authors":"Sotaro Kusumoto, Kippei Usuda, Kenta Rakumitsu, Yang Kim and Yoshihiro Koide","doi":"10.1039/D5CE00203F","DOIUrl":"https://doi.org/10.1039/D5CE00203F","url":null,"abstract":"<p >Photo-salient metal chloride-templated organic–inorganic hybrid crystals incorporating (<em>E</em>)-1,2-bis(pyridin-4-yl)ethene (<strong>Ebpe</strong>) exhibited pronounced photo-salient effects, demonstrably jumping upon UV-induced [2 + 2] photodimerization. Detailed structural analysis reveals that the metal chloride component is an effective template, precisely aligning <strong>Ebpe</strong> molecules for efficient photodimerization. This work provides a rare example of a metal halide facilitating [2 + 2] photodimerization and establishes a new pathway for developing photosalient materials with tailored reactivity.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 19","pages":" 2993-2997"},"PeriodicalIF":2.6,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143944045","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":"Enhancement of visible-light-driven photocatalytic oxidative amine coupling through light-induced carrier spatial separation†","authors":"Xiying Zhang, Yuanyuan Li, Zhaozhen Zhang, Bin Zhang, Xiaomeng Hu, Shibo Lu and Jie Wu","doi":"10.1039/D5CE00233H","DOIUrl":"https://doi.org/10.1039/D5CE00233H","url":null,"abstract":"<p >Efficient charge separation and utilization are critical factors in photocatalysis, especially for photocatalytic oxidative amine coupling, which utilizes both electrons and holes to obtain reactive oxygen species. Herein, a Pt@UiO-66-NH<small>₂</small>-OH@Cu<small>₂</small>O composite, featuring spatial separation of reduced Pt nanoparticles (NPs) and oxidized Cu<small>₂</small>O NPs with defect-engineered UiO-66-NH<small>₂</small>-OH, is reported for enhancing visible-light-driven photocatalytic oxidation of amines. The Pt NPs embedded in the MOF pores act as electron collectors, while the Cu<small>₂</small>O NPs covering the surface of the MOF serve as hole collectors. This spatial separation effectively directs the electron and hole flow, reduces electron–hole recombination and enhances the charge separation efficiency. Besides, the highly porous structure of Pt@UiO-66-NH<small>₂</small>-OH@Cu<small>₂</small>O exhibits confined cavities and high surface area and can reduce the kinetic resistance to substrate and product diffusion. Therefore, Pt@UiO-66-NH<small>₂</small>-OH@Cu<small>₂</small>O exhibits excellent photocatalytic activity for the oxidation of benzylamine to obtain <em>N</em>-benzyl-1-phenylmethanimine as the solo product and achieve a high conversion rate of 99% under low-energy LED light.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 21","pages":" 3584-3593"},"PeriodicalIF":2.6,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144140049","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":"Diverse tetracyanodihydrodipyrazinopyrazine clathrate crystals assembled from weak intermolecular interactions†","authors":"Kosuke Watanabe, Haruki Sugiyama and Yasutomo Segawa","doi":"10.1039/D5CE00289C","DOIUrl":"https://doi.org/10.1039/D5CE00289C","url":null,"abstract":"<p >Tetracyanodihydrodipyrazinopyrazines with two mesityl (2,4,6-trimethylphenyl) groups formed clathrate crystals with 15 kinds of organic solvents. Two common types of host molecular networks were observed in the crystals. Theoretical calculations indicated that these host networks are constructed from π–π and CN–π interactions. As these intermolecular interactions are relatively weak, the host network can change flexibly in response to guest molecules. Guest-free crystals can be reversibly transformed into clathrate crystals through crystal-to-crystal phase transitions <em>via</em> the adsorption/desorption of solvent vapor.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 21","pages":" 3552-3559"},"PeriodicalIF":2.6,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ce/d5ce00289c?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144140043","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":"Embedding crystalline Cu and Cu2O nanoparticles in silicate glasses through an ion-exchange process followed by gamma irradiation and annealing: an optical absorption spectroscopy assessment","authors":"Safa Toumi, Khaled Farah and Alaa Adawy","doi":"10.1039/D4CE01225A","DOIUrl":"https://doi.org/10.1039/D4CE01225A","url":null,"abstract":"<p >Studies focusing on finding methodologies to obtain nanocrystalline structures in the form of nanoparticles have gained significant interest in the last two decades, given their broad possibilities to serve in different technological applications, and those related to glass technology are not an exception. Different routes are utilized to characterize crystalline nanoparticle growth. Hereby, an ion-exchange process followed by gamma ray irradiation and/or annealing treatment was used to effectuate the growth of copper nanoparticles (CuNPs) in glass matrices. Relying on well-established optical absorption spectroscopy, a precise and timely analysis of the changes occurring in the glass matrix, along with the formation of the CuNPs, defining their oxidation state and their sizes was performed. The study revealed that the formation of CuNPs in the glass matrix takes place within an unexpectedly short duration after the ion-exchange process. Irradiating the Cu-exchanged glass with gamma rays at ≈100 kGy increased the CuNPs formation and volume fraction, whereas at higher doses ≈1000 kGy the formed nanoparticles had smaller sizes. Interestingly, combining γ-irradiation with annealing for the Cu-exchanged glasses resulted in either size growth of CuNPs or their partial or total oxidation and their conversion to the more stable and ecofriendly Cu<small>₂</small>O nanoparticles.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 21","pages":" 3444-3455"},"PeriodicalIF":2.6,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ce/d4ce01225a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144140022","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":"Tunable ellipsoidal cage in ZIF-300 and ZIF-301 for size-selective acetone/butanol separation†","authors":"Yanjun Wu, Jiaojiao Song, Jiang Wang and Qi Shi","doi":"10.1039/D5CE00258C","DOIUrl":"https://doi.org/10.1039/D5CE00258C","url":null,"abstract":"<p >In this work, ZIF-300 and ZIF-301 derivatives with tunable ellipsoidal cage sizes were synthesized by adjusting the ratio between the small-sized mIm and large-sized bbIm/cbIm ligands. During ZIF synthesis, when the amount of the fixed ligand is equimolar to Zn<small>²⁺</small>, adjusting the content of the other ligand does not yield a continuously tunable structure. In contrast, maintaining an excess of one ligand relative to Zn<small>²⁺</small> and varying the content of the other ligand enables the formation of ZIF derivatives with continuously tunable chemical compositions and ellipsoidal cage sizes. This tunability is likely due to the increased concentration of the fixed ligand, which enhances its competitive coordination ability within the ZIF framework. Consequently, ZIF-300 and ZIF-301 derivatives with adjustable long-axis cage sizes ranging from 6.5 Å to 9.6 Å were successfully prepared. Notably, the small cage-sized ZIF-300-S1 (6.5 × 6.1 Å<small>²</small>) and ZIF-301-S1 (6.5 × 6.6 Å<small>²</small>) exhibited exceptional molecular length separation of acetone (6.4 × 5.8 Å<small>²</small>) and butanol (8.4 × 5.5 Å<small>²</small>). Liquid-phase adsorption and breakthrough experiments confirmed their separation performance, and GCMC simulations provided further insights into the separation mechanism.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 21","pages":" 3566-3575"},"PeriodicalIF":2.6,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144140047","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}